TWI410280B - Metal complexes - Google Patents

Abstract

The invention concerns metal complexes and their preparation, in particular a metal complex MLnXm, where M is a metal of group 8, 9 or 10 and X is a halide, HCO3-, NO3-, CO32- or carboxylate. n is a number equal to or less than the coordination number of the metal and m is 1 or 2 and is equal to the oxidation state of the metal. The ligand L may be a bidentate phosphine of formula (I), (II), (III) or (IV) as set out herein. The process of production comprises reacting an ammine compound of metal M with a complexing compound, which is preferably a phosphine.

Description

Metal complex

This invention relates to stable metal complexes useful for the carbonylation of ethylenically unsaturated compounds, and to their preparation.

The invention also relates to novel catalyst systems incorporating such complexes.

a ethylenically unsaturated compound using carbon monoxide in an alcohol or water, and comprising a Group 6, 8, 9 or 10 metal such as palladium, and a phosphine ligand such as an alkylphosphine, a cycloalkylphosphine, an arylphosphine, a pyridine The carbonylation in the presence of a phosphine or a bidentate phosphine catalyst system has been described in a number of European patents and patent applications, for example, EP-A-0 055 875, EP-A-04489472, EP-A-0106379, EP-A-0235864, EP-A-0274795, EP-A-0499329, EP-A-0386833, EP-A-0441447, EP-A-0489472, EP-A-0282142, EP-A-0227160, EP- A-0495547 and EP-A-0495548. In particular, EP-A-0227160, EP-A-0495547 and EP-A-0495548 disclose bidentate phosphine ligands which provide a catalyst system capable of achieving high reaction rates. The C3 alkyl bridging group between the phosphorus atoms is exemplified in EP 0495548 as a third butyl substituent on the phosphorus.

WO 96/19434 then discloses a specific group of bidentate phosphine compounds having substituted aryl bridging groups which provide a significant stabilization catalyst with little or no need for replenishment; use of such bidentate catalysts It can result in a significantly higher reaction rate than previously disclosed; and produces little or no impurities at high conversions.

WO 01/68583 discloses the rate of the same method as in WO 96/19434 when used in higher olefins and in the presence of an externally added aprotic solvent.

EP 0 495 548 B1 is an example of the vinylation of vinyl acetate using a C3 bridged phosphine 1,3-bis(di-tert-butylphosphino)propane. The rate quoted was 200 moles per hour of Pd per mole and the result was the production of propionate 1 and 2-ethoxymethoxymethyl ester in a ratio of 40:60 (linear: branched).

WO 98/42717 discloses the modification of the bidentate phosphine used in EP 0 495 548, in which one or two phosphorus atoms are incorporated into a optionally substituted 2-phosphorus tricyclic [3.3.1.1 {3,7 In the thiol group or a derivative thereof, one or more of the carbon atoms are replaced by a hetero atom ("2-PA" group). Examples include ethylene, propylene, and some alkoxycarbonylation of some high carbon ends with internal olefins. In addition, the hydroformylation of vinyl acetate is also revealed, and a 10:1 branched: linear product ratio is obtained. It is worth noting that the alkoxy or hydroxy-carbonylation of vinyl acetate is not disclosed.

WO 03/070370 extends the disclosure of WO 98/42717 to didentate phosphines having one or two substituted aryl bridging groups of the type disclosed in WO 96/19434. Suitable olefin acceptor systems disclosed include several types having different substituents. It is worth noting that vinyl esters are not mentioned, either generically or specifically.

WO 04/103948 describes that two of the above types of ligand bridging can be used for butadiene carbonylation, while WO 05/082830 describes an option of WO 04/103948 in which tertiary carbon substituents are Individual phosphorus atoms are different.

Nonetheless, all of the above systems require the manufacture of metal coordination complexes from ligands with metals or metal compounds under carefully controlled conditions, since the ligand-metal complex is unstable in air. However, the use of a stable metal compound provides a possible source of catalyst poisoning, or at least a waste product in the form of a metal anion and/or salt. In time, this agent, which has been provided with a source of metal stability, is accumulated in the catalyst system and must be periodically removed. The present invention solves this problem by providing a stable catalyst metal complex having an easily treatable by-product.

According to a first aspect of the present invention, there is provided a metal complex ML _n X _m wherein M is a metal of Group 8, 9 or 10, L is a ligand, and X is a halide, HCO ₃ ^- , NO ₃ ^- , CO ₃ ^2- or carboxylate, n is the number equal to or less than the metal coordination number, m is 1 or 2, and is equal to the oxidation state of the metal.

For the avoidance of doubt, references to Group 8, 9 or 10 metals herein shall be taken to include Groups 8, 9 and 10 of the Modern Periodic Table nomenclature. The term "Group 8, 9 or 10" is preferred for metals such as Ru, Rh, Os, Ir, Pt and Pd. Preferably, the metal is selected from the group consisting of Ru, Pt and Pd. This metal is more preferably Pd.

Typically, the number n is between 1-6, more typically 1-4, especially 1 or 2, more especially 2. A particularly good metal complex is one in which the amino group has been removed. It has been surprisingly and expediently found that this is possible when the dihydrocarbonate complex is further heated during misalignment with the metal. It has been found that after heating, the dihydrocarbonate complex can be rearranged internally to produce ammonium carbonate and bidentate carbonate species. This advantageously produces a metal complex ML _n X wherein X is a bidentate carbonate ligand and M, L and n are all defined herein.

The ligand L is preferably a phosphine, and thus the compound is a phosphine. The phosphine can be a monodentate or a bidentate phosphine. Tertiary phosphines are preferred and may be selected from triphenylphosphines other than those of formula (I)-(V) generally herein; 2,2'-bis[bis(3,5-dimethylbenzene) Phosphyl]-1,1'-binaphthyl; 1,4-bis[bis(3,5-dimethylphenyl)phosphino]butane; 1,2-bis[double(3,5-) Dimethylphenyl)phosphino]ethane; bis[bis(3,5-dimethylphenyl)phosphino]methane; 1,3-bis[bis(3,5-dimethylphenyl)phosphine Propane; 2,2'-bis[bis(3,5-bistrifluoromethylphenyl)phosphino]-1,1'-binaphthyl; 1,4-double [double (3,5-double) Trifluoromethylphenylphosphinyl]butane; 1,3-bis[bis(3,5-bistrifluoromethylphenyl)phosphino]propane; 1,2-bis[double (3,5-) Bis(trifluoromethylphenyl)phosphino]ethane; tris(tert-butyl)phosphine; 1,2-bis(di-tert-butylphosphinomethyl)benzene; 1,2-bis(di -T-butylphosphino)benzene; 2,2'-bis(di-tertiary-butylphosphino)biphenyl; 1,4-bis(di-tertiary-butylphosphino)butane; 1,3-bis(di-tert-butylphosphinomethyl)propane; 1,3-bis(di-tertiary-butylphosphino)propane; 1,2-bis(di-third-butyl) Ethylphosphine) ethane; 1,1'-bis (di-third-butyl) Phosphyl)dicyclopentadienyl iron; bis(di-tertiary-butylphosphino)methane; 1,3-bis(di-tertiary-butylphosphinomethyl)benzene; cis (p-tolyl) Phosphine; cis (o-tolyl)phosphine; tricyclohexylphosphine; 1,2-bis(dicyclohexylphosphino)benzene; 2,2'-bis(dicyclohexylphosphino)biphenyl; 1,4 - bis(dicyclohexylphosphino)butane; 1,3-bis(dicyclohexylphosphino)propane; 1,2-bis(dicyclohexylphosphino)ethane; 1,1'-bis (bicyclic) Hexylphosphino)dicyclopentadienyl iron; 1,1'-bis(diisopropylphosphino)dicyclopentadienyl iron; 1,2-bis(diisopropylphosphino)benzene; 1,3 - bis(diisopropylphosphino)propane; 1,2-bis(diisopropylphosphino)ethane; 1,4-bis(dimethylphosphino)butane; 1,3-double (two Methylphosphinomethyl)benzene; 1,2-bis(dimethylphosphino)benzene; 2,2'-bis(dimethylphosphino)biphenyl; 1,3-bis(dimethylphosphino) Propane; 1,2-bis(dimethylphosphino)ethane; 1,1'-bis(dimethylphosphino)dicyclopentadienyl iron; 1,4-bis(dimethylphosphino) Butane; 1,2-bis(di-phenylphosphinomethyl)benzene; 1,3-bis(diethylphosphinomethyl)benzene; 1,2-bis(diethylphosphino)benzene; 2,2' - bis(diethylphosphino)biphenyl; 1,3-bis(diethylphosphino)propane; 1,2-bis(diethylphosphino)ethane; 1,1'-bis(diphenyl Alkylphosphino)dicyclopentadienyl iron; and 1,1'-bis(diethylphosphino)dicyclopentadienyl iron.

More preferably, when the ligand L is a bidentate phosphine ligand, more particularly a bidentate phosphine ligand of the formula (I), (II), (III), (IV) or (V), It will be more specifically described herein. Furthermore, as stated above, the particularly preferred bidentate phosphine ligand for this point is ML-LX, wherein L-L is a bidentate phosphine ligand, M is a metal, and X is a bidentate carbonate . In this regard, the more preferred metal is palladium.

According to a second aspect of the present invention, there is provided a process for the carbonylation of an ethylenically unsaturated compound which comprises reacting the compound with a carbon monoxide in the presence of a co-reactant and a catalytic system having an active hydrogen such as a hydroxyl group. In response, the catalyst system is derived from a metal complex according to the first aspect of the invention.

Such complexes are advantageously (1) no heavy accumulation, (2) no air sensitivity, and (3) reduced catalyst preparation time.

1. No heavy accumulation in the Pd(0) production system, such as the Pd(dba) catalyst system, and dba is a harmless ligand. It plays a role in the stabilization of palladium zero precursors, but does not have a catalytic function. The activation of the sulfonic acid catalyst results in the release of dba into the treatment solution. The concentration in the reactor will accumulate and, finally, the scrubbing of the catalyst recycle stream is required to stop the accumulation to the point where it has a deleterious effect on the process. The combined palladium ligand salts (especially bicarbonates, carbonates, acetates, and lactates) do not produce heavy components upon activation with a suitable acid such as a sulfonic acid. The best option is that bicarbonate and carbonate will produce CO ₂ and water upon activation, both of which will not interfere with the process chemistry to the extent possible.

2. No Air Sensitivity In any full scale method design, a catalyst preparation system would be required in which the coordination system is combined with the palladium salt and acid prior to being fed to the reactor. The phosphine ligands of the prior art methods mentioned above are extremely air sensitive in solution, so to avoid unwanted oxidation of the phosphine, a highly degassed solvent is required. The effective removal of oxygen from organic solvents to sub-ppm levels is desirable, and subsequent analysis is a challenge on a large scale. The combined ligand palladium salt of the present invention is not air sensitive and can be dissolved in a less severely degassed solvent.

3. Reduced Catalyst Preparation Time The Pd(0) generation system, such as the Pd(dba) catalyst system, spends approximately 48 hours of mismatching and activation. During the first 24 hours of this process, free state ligands are present and the system is sensitive to oxidation. The catalyst solution using the palladium ligand salt of the present invention can be produced in only 1-2 hours by merely slurrying the complex in MeP/MeOH and adding a suitable acid such as a sulfonic acid. The catalytic species formed in this method are the same as those formed by the Pd(dba) catalyst system.

It has also been found that the metal complex of the present invention is more air stable than the equivalent metal dba complex and also exists in a catalytically active state, whereas the metal dba complex is in a non-catalytic oxidation state. One problem with prior art catalysts is that the phosphine ligand must be added separately to the reaction chamber in the presence of a degassed solvent. The phosphine coordination system is highly air sensitive, so the solvent used in the continuous process must be completely degassed beforehand so that the phosphine is not oxidized prior to metal mismatch. If the phosphine ligand is oxidized, the ligand becomes inactive and will not mismatch to the metal to form the active catalyst. By forming the stability complex of the present invention, such additional steps can be avoided in industrial processes for catalyst utilization.

According to a further aspect of the invention there is provided a catalyst system capable of carbonylating an ethylenically unsaturated compound comprising a metal complex according to the first aspect of the invention.

Suitable acids for use in the catalyst system of the present invention are known to those skilled in the art. Suitable acids include nitric acid; sulfuric acid; lower alkanonic acid (up to C ₁₂ ) acids such as acetic acid and propionic acid; sulfonic acids such as methanesulfonic acid, chlorosulfonic acid, fluorosulfonic acid, trifluoromethanesulfonic acid, benzenesulfonate Acid, naphthalenesulfonic acid, toluenesulfonic acid, such as p-toluenesulfonic acid, tert-butylsulfonic acid, and 2-hydroxypropanesulfonic acid; sulfonated ion exchange resin (including low acid content sulfonic acid resin), Perhalogen acids, such as perchloric acid; halogenated carboxylic acids such as trichloroacetic acid and trifluoroacetic acid; orthophosphoric acid; phosphonic acid, such as phenylphosphonic acid; and acids derived from the interaction between Lewis acid and Broensted acid.

In the alkoxycarbonylation reaction, the acid may have a pKa of less than 4, more preferably less than 3, as measured in an aqueous solution at 18 °C. Suitable acids include those other than the unsubstituted carboxylates listed above.

In the hydroxycarbonylation reaction, the acid may have a pKa of less than 6, more preferably less than 5, as measured in an aqueous solution at 18 °C. Suitable acids include the acids listed above.

In a particularly preferred embodiment, the acid in the hydroxycarbonylation reaction can be derived from a carboxylic acid. The carboxylic acid is preferably any optionally substituted C ₁ -C ₃₀ organic compound having at least one carboxylic acid group, more preferably any C1 to C16 organic compound having at least one carboxylic acid group. The pKa of the acid is measured in an aqueous solution at 18 ° C, preferably greater than about 2. The pKa measured in an aqueous solution at 18 ° C is preferably less than about 5.0. The organic compound may be substituted by one or more of the following: a hydroxyl group, a C ₁ -C ₄ alkoxy group such as a methoxy group; an amine, or a halide group such as Cl, I and Br. Examples of suitable carboxylic acids include, but are not limited to, benzoic acid, substituted benzoic acid, acetic acid, propionic acid, valeric acid, butyric acid, cyclohexylpropionic acid, 2,3 or 4-pentenoic acid, adipic acid or citric acid. .

Examples of suitable sterically hindered carboxylic acids which may be employed in the hydroxycarbonylation reaction include, but are not limited to, sterically hindered benzoic acids, including, for example, C ₁ -C ₄ alkyl substituted benzoic acids, such as 2,6 -Dimethylbenzoic acid or 2,4,6-trimethylbenzoic acid. It also includes hydroxy-substituted benzoic acids such as meta- and para-hydroxybenzoic acid, and other substituted benzoic acids such as 2,6-difluorobenzoic acid or 2,4,6-tribromobenzoic acid.

A particularly preferred acid promoter for alkoxycarbonylation is a sulfonic acid and a sulfonated ion exchange resin as set forth above. A low level of acid ion exchange resin may be used, preferably to provide a ratio of SO ₃ H/Pd in the reaction to less than 35 moles per mole, more preferably less than 25 moles per mole, and the optimum is low. At 15 m / m. SO ₃ H typical range of concentration provided by the resin, based on the range of 1-40 mole / mole of Pd, more typically the molar is most typically on 2-30 mole Pd / 3-20 Moor/Mor Pd.

In the hydroxycarbonylation reaction, the solvent may preferably have an acid having a pKa of less than 5, more preferably a pKa of more than 3 and less than 5. Alternatively a suitable acid solvent listed hereinbefore acids from the front, more preferably lower alkyl (up to C ₁₂₎ acids, such as acetic acid and propionic acid, most preferably acetic acid.

In the alkoxycarbonylation reaction, the amount of acid present is not critical to the catalytic behavior of the catalyst system. The molar ratio of the acid to the Group 8, 9 or 10 metal or compound may range from 1:1 to 500:1, preferably from 2:1 to 100:1, and especially from 3:1 to 30:1. Preferably, the ratio of acid to Group 8, 9 or 10 metal is preferably at least 1:1 moles (H ⁺ ) / moles (C ²⁺ ), and preferably less than at least 5:1 moles (H ⁺ ) / Mohr (C ²⁺ ), more preferably, the ratio is at least 2:1, and preferably less than at least 3:1; optimally, a ratio of about 2:1 is preferred. The H ⁺ system means the amount of active acidic sites, so the 1 moler base acid has 1 mol H ⁺ , whereas the 1 mol 2 salt acid has 2 mol H ⁺ and the tris Acids, etc., should be interpreted accordingly. Similarly, the C ²⁺ system means the number of moles of a metal having a 2 ⁺ cationic charge, so the ratio of the metal cation to the M ⁺ ion should be adjusted accordingly. For example, the M ⁺ cation should be taken to have 0.5 mole C ²⁺ per mole of M ⁺ .

In the hydroxycarbonylation reaction, the amount of acid present is not critical to the catalytic behavior of the catalyst system. The molar ratio of acid to Group 8, 9 or 10 metal/compound may range from 1:1 to 10000:1, preferably from 2:1 to 1000:1, and especially from 3:1 to 100:1.

In the alkoxycarbonylation reaction, the ratio of bidentate ligand to acid is preferably at least 1:2 moles/mole (H ⁺ ), and the bidentate ligand is for groups 8, 9 or 10 The proportion of metal is preferably at least 1:1 mol/mole (C ²⁺ ). The ligand preferably exceeds the metal moles/mole (C2 ⁺ ) and preferably exceeds the 1:2 molar/mole (H ⁺ ) ratio of the acid. Excess ligands are advantageous because the ligand itself can act as a base to buffer the acid content of the reaction and prevent degradation of the substrate. On the other hand, the presence of an acid activates the reaction mixture and improves the overall reaction rate.

In the hydroxycarbonylation reaction, the ratio of bidentate ligand to acid is preferably at least 1:2 moles/mole (H ⁺ ), and the bidentate ligand is for Group 8, 9 or 10 metals. The ratio is preferably at least 1:1 mole/mole (C2 ⁺ ). Preferably, the ligand is in excess of metal moles/mole (C2 ⁺ ). Excess ligand may be advantageous because the ligand itself may act as a base to buffer the acid content of the reaction and prevent degradation of the substrate. On the other hand, the presence of an acid activates the reaction mixture and improves the overall reaction rate.

According to a further aspect of the present invention there is provided a process for the carbonylation of an ethylenically unsaturated compound comprising the step of reacting the compound in a solvent system comprising a carboxylic acid, preferably an aromatic carboxylic acid, a catalyst system And reacting with carbon monoxide and a co-reactant having active hydrogen in the presence of a source of hydrogen selected, the catalyst system comprising a metal complex according to the first aspect of the invention.

The co-reactant of the present invention may be any compound having a mobile hydrogen atom and capable of reacting with a diene as a nucleophile under catalytic conditions. The chemical nature of the co-reactant determines the type of product formed. A particularly advantageous co-reactant is water, so hydroxycarbonylation is preferred. However, other co-reactants may also be employed, and may be advantageous, such as carboxylic acids, alcohols, ammonia or amines, thiols, or combinations thereof. If the co-reactant is water, the product obtained will be an unsaturated carboxylic acid. In the case of carboxylic acids, the product is an unsaturated anhydride. For alcohol co-reactants, the product of carbonylation is an ester.

Similarly, the use of ammonia (NH ₃ ), or a primary or secondary amine, R ⁸¹ NH ₂ or R ⁸² R ⁸³ NH, will produce a guanamine, while the use of a thiol R ⁸¹ SH will result in a thioester. In the co-reactants defined above, R ⁸¹ , R ⁸² and/or R ⁸³ represent an alkyl group, an alkenyl group or an aryl group which may be unsubstituted or may be substituted by one or more substituents. The group is selected from the group consisting of halo, cyano, nitro, OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , SR ²⁹ , C(O)SR ³⁰ , C(S)NR ²⁷ R ²⁸ , aryl or Het, wherein R ¹⁹ to R ³⁰ are each as defined herein, and/or are one or more oxygen or sulfur atoms or are A decyl or dialkyl fluorenyl group is inserted.

If ammonia or an amine is used, a small portion of the co-reactant will react with the acid present in the reaction to form the guanamine and water. Thus, in the case of ammonia or an amine-co-reactant, the water system is present.

The carboxylic acid co-reactant preferably has the same number of carbon atoms as the diene reactant plus one.

Preferred amine co-reactant systems have from 1 to 22, more preferably from 1 to 8 carbon atoms, and diamine co-reactants - from 2 to 22, more preferably from 2 to 10 carbon atoms per molecule. . The amines may be cyclic, partially cyclic, fluorenyl, saturated or unsaturated (including aromatic), unsubstituted or substituted by one or more substituents selected from halo, cyano, nitro , OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , SR ²⁹ , C(O)SR ³⁰ , C (S)NR ²⁷ R ²⁸ , aryl, alkyl, Het, wherein R ¹⁹ to R ³⁰ are as defined herein, and/or are one or more (preferably less than a total of 4) oxygen, nitrogen, sulfur , a ruthenium atom or inserted by a decyl or dialkyl fluorenyl group, or a mixture thereof.

The thiol co-reactant may be cyclic, partially cyclic, fluorenyl, saturated or unsaturated (including aromatic), unsubstituted or substituted by one or more substituents selected from halo, cyano , nitro, OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , SR ²⁹ , C(O)SR ³⁰ , C(S)NR ²⁷ R ²⁸ , aryl, alkyl, Het, wherein R ¹⁹ to R ³⁰ are as defined herein, and/or are one or more (preferably less than a total of 4) oxygen, Nitrogen, sulfur, helium atoms or are inserted by a decyl or dialkyl fluorenyl group or a mixture thereof. Preferred thiol co-reactants are aliphatic thiols having from 1 to 22, more preferably from 1 to 8 carbon atoms, and from aliphatic dithiols having from 2 to 22 per molecule, more Preferably 2 to 8 carbon atoms.

If the co-reactant will react with the acid, the amount of acid to co-reactant should be selected such that an appropriate amount of free acid is present. In general, excess acid which is larger than the total amount of the co-reactant is preferred because of the increased reaction rate.

The carboxylic acid used in this aspect of the invention may be any optionally substituted C ₁ -C ₃₀ compound additionally having at least one carboxylic acid group, more preferably any C ₁ to C having at least one carboxylic acid group. ₁₆ compounds. The pKa of the acid is measured in a dilute aqueous solution at 18 ° C, preferably greater than about 2. The pKa is measured in a dilute aqueous solution at 18 ° C, preferably less than about 6. Examples of suitable carboxylic acids include: C ₁ -C ₁₂ alkanoic acids which are optionally substituted, such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, decanoic acid; C ₁ -C ₁₂ enoic acids, such as acrylic acid , for example, acrylic acid, crotonic acid, such as methacrylic acid, pentenoic acid, hexenoic acid and heptenoic acid; lactic acid; where possible, all of them may be linear or branched, cyclic, partially cyclic Or acyclic, and in addition to being intervened by a hetero atom, may be unsubstituted or substituted by one or more other substituents selected from aryl, alkyl, heteroatoms (preferably oxygen) , Het, halo, cyano, nitro, -OR ¹⁹ , -OC(O)R ²⁰ , -C(O)R ²¹ , -C(O)OR ²² , -N(R ²³ )R ²⁴ , C (O)N(R ²⁵ )R ²⁶ , -SR ²⁹ , -C(O)SR ³⁰ , -C(S)N(R ²⁷ )R ²⁸ or -CF ₃ , wherein R ¹⁹ -R ²⁸ are as defined herein . The particularly preferred carboxylic acid is the acid product of the carbonylation reaction.

The aromatic carboxylic acid used in the carbonylation reaction, such as the hydroxycarbonylation reaction, is preferably any optionally substituted C ₁ -C ₃₀ aromatic compound, such as a phenyl, naphthyl or cyclopentadienyl anion. And a mercapto group having a mercapto group, a pyridyl group and a pyrrolyl group, and having at least one carboxylic acid group bonded to the aromatic ring, more preferably any C ₁ to C ₁₆ aromatic compound having at least one carboxylic acid group. The pKa of the acid is measured in a dilute aqueous solution at 18 ° C, preferably greater than about 2. The pKa is measured in a dilute aqueous solution at 18 ° C, preferably less than about 6, more preferably less than 5.

The carboxylic acid group means a -COOH group, and it may be directly bonded to the cyclic ring atom of the aromatic ring, but may also be attached to the alpha or beta carbon of the ring, more preferably attached to the alpha carbon or Directly to the ring, it is best to connect directly to the ring.

The aromatic compound may be substituted by one or more of the following: alkyl; aryl; hydroxy; alkoxy, such as methoxy; amine, or halo, such as F, Cl, I and Br.

The aromatic ring of the carboxylic acid can be substituted on any of the available nitrogen atoms. The aromatic ring is preferably mono- or di-substituted. Examples of suitable aromatic carboxylic acids include benzoic acid; naphthoic acid; and cyclopentadienoic acid, particularly preferably substituted aromatic acids, including, for example, C ₁ -C ₄ alkyl substituted benzoic acids, such as 2,4,6-trimethylbenzoic acid or 2,6-dimethylbenzoic acid, and o-methylbenzoic acid (2-methylbenzoic acid), 2-nitrobenzoic acid, 6-chloro- 2-Hydroxymethylbenzoic acid, 4-aminobenzoic acid, 2-chloro-6-hydroxybenzoic acid, 2-cyanobenzoic acid, 3-cyanobenzoic acid, 4-cyanobenzoic acid, 2,4-dihydroxy Benzoic acid, 3-nitrobenzoic acid, 2-phenylbenzoic acid, 2-tris-butylbenzoic acid, 2-naphthoic acid, 1-naphthoic acid, 2,4-dimethylbenzoic acid, 3-methyl Benzoic acid, 3,5-dimethylbenzoic acid, 4-hydroxybenzoic acid, 2-fluorobenzoic acid, 3-propoxybenzoic acid, 3-ethoxybenzoic acid, 2-propoxybenzoic acid, 2,2-diphenylpropionic acid, 2-methoxyphenylacetic acid, o-anisic acid, m-anisic acid, 4-tris-butylbenzoic acid, and 2-ethoxybenzoic acid.

In addition to the group bearing a carboxylic acid, the aromatic carboxylic acid is preferably substituted with only one group. The alkyl group is preferably an aromatic ring substituted for the carboxylic acid. A particularly preferred compound is o-methylbenzoic acid.

Preferably, when the solvent system comprises a carboxylic acid (preferably an aromatic carboxylic acid) as defined above, at least one cosolvent is also used. Suitable cosolvents include the aprotic solvents mentioned herein.

The invention also relates to the preparation of metal complexes, particularly noble metal phosphine complexes.

The noble metal β-diketonate, such as palladium(II) acetylacetonate, is used in many chemical processes as a catalyst or as a component of a catalyst system. Palladium(II) acetate pyruvate has been prepared from palladium (II) chloride. For example, GB-A-1475834 describes a process comprising dissolving PdCl ₂ or a miscible tetrachloropalladium salt in hydrochloric acid, reacting the formed solution with at least a stoichiometric amount of acetamidine, and stirring the mixture to a transparent The solution was then adjusted to pH 8 from 7 by gradually adding an aqueous alkali metal hydroxide solution to separate the precipitated acetylpyruvate Pd(II), which was washed and dried.

The process of the present invention provides a process for preparing a metal complex which does not use a metal dichloride as a starting material. Since MCl ₂ is usually prepared from an amine compound by calcination/reduction to a metal sponge, followed by reaction with chlorine and hydrochloric acid, the use of the process of the present invention avoids such additional processing steps and has environmental benefits.

One item of the present invention is to provide an alternative method of preparing a noble metal complex such as a noble metal phosphine.

According to a further aspect of the present invention, there is provided a process for the preparation of a metal complex ML _n X _m wherein M is a metal atom, L is a ligand, and X is a halide, HCO ₃ ^- , NO ₃ ^- , CO ₃ ^{2 -} or carboxylate, n-number of equal to or less than the coordination number of the metal, m is 0, 1 or 2, and is equal to the oxidation state of the metal, which comprises reacting an amine compound of the metal m with wrong bonding compound.

When M is palladium, it may be Pd(II) or Pd(0). Therefore, in the case of palladium complex production, m is 2 or 0.

The metal amination can be an ionic compound. In this case, the anion is preferably selected from the group consisting of a halide (preferably a chloride), a bicarbonate, a carbonate, a carboxylate (such as acetate, lactate or citrate) or a nitrate. Suitable palladium aminations include Pd(NH ₃ ) ₂ Cl ₂ , Pd(NH ₃ ) ₄ (HCO ₃ ) ₂ , Pd(NH ₃ ) ₄ (CH ₃ CO ₂ ) ₂ , Pd(NH ₃ ) ₄ (NO ₃ ) ₂ . Pd(NH ₃ ) ₂ Cl ₂ , Pd(NH ₃ ) ₄ (HCO ₃ ) ₂ and Pd(NH ₃ ) ₄ (CH ₃ CO ₂ ) ₂ are particularly preferred metal aminations.

Particularly preferred is the reaction of Pd(NH ₃ ) ₄ (HCO ₃ ) ₂ with a ligand as defined herein, 二 a bidentate ligand as set forth below. In a preferred reaction, the bidentate ligand is reacted with a Pd(NH ₃ ) ₄ (HCO ₃ ) ₂ complex in a suitable solvent such as methanol and heated for several hours, typically over 2 hours. And less than 12 hours, more typically 4-8 hours. This prolonged heating causes the formation of bidentate carbonate, which is typically ammonium bicarbonate with the release of ammonia. This ammonium hydrogencarbonate may be left in solution accompanying precipitation of the desired metal complex or may be removed by water washing or extraction because ammonium hydrogencarbonate is soluble in water. Advantageously, improvements in TON with respect to such metal complexes have been found, and this may be due to the absence of ammonia in the final metal complex.

As mentioned herein, in a specific embodiment of the invention, the bidentate phosphine coordination system has the general formula (I) Wherein: Ar is a bridging group comprising an optionally substituted aryl moiety, the phosphorus atom is bonded to the group at adjacent carbon atoms; and A and B each independently represent a lower alkylene group. ; K, D, E and Z are substituents of the aryl moiety (Ar), and each independently represents hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , C(S)R ²⁵ R ²⁶ , SR ²⁷ , C(O SR ²⁷ or -J-Q ³ (CR ¹³ (R ¹⁴ )(R ¹⁵ )CR ¹⁶ (R ¹⁷ )(R ¹⁸ ), wherein J represents a lower alkylene group; or is selected from K, Z, D and E Two adjacent groups, together with the carbon atoms of the aryl ring to which they are attached, form another phenyl ring, which is optionally substituted with one or more substituents selected from hydrogen, lower alkyl , halo, cyano, nitro, OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , C( S) R ²⁵ R ²⁶ , SR ²⁷ or C(O)SR ²⁷ ; R ¹³ to R ¹⁸ each independently represent hydrogen, lower alkyl, aryl or Het, preferably each independently represents lower alkyl, aryl Or Het; R ¹⁹ to R ²⁷ are independent Represents hydrogen, lower alkyl, aryl or Het; R ¹ to R ¹² each independently represent hydrogen, lower alkyl, aryl or Het, preferably each independently represents lower alkyl, aryl or Het; ¹ , Q ² and Q ³ (when present) each independently represent phosphorus, arsenic or antimony, and in the latter case, the reference to the above phosphine or phosphorus is modified accordingly, wherein both Q ¹ and Q ² Preferably, phosphorus is present, and more preferably all of Q ¹ , Q ² and Q ³ (when present) represent phosphorus.

Suitably, the bidentate phosphine of the present invention should preferably be capable of bidentate coordination to a Group VIB or Group VIIIB metal or compound thereof, more preferably to a preferred palladium.

When K, D, E or Z represents -J-Q ³ (CR ¹³ (R ¹⁴ )(R ¹⁵ ))CR ¹⁶ (R ¹⁷ )(R ¹⁸ ), individual K, D, E or Z is preferably attached to On the aryl carbon, adjacent to the aryl carbon to which A or B is attached, or if not adjacent, is adjacent to itself to represent -J-Q ³ (CR ¹³ (R ¹⁴ )(R ¹⁵ )) CR ¹⁶ (R ¹⁷ ) The remaining K, D, E or Z groups of (R ¹⁸ ).

Specific, but non-limiting examples of bidentate ligands in this particular embodiment include the following: 1,2-bis-(di-tertiary-butylphosphinomethyl)benzene, 1,2-double -(di-t-pentylphosphinomethyl)benzene, 1,2-bis-(di-tertiary-butylphosphinomethyl)naphthalene. Nonetheless, it will be apparent to those skilled in the art that other bidentate ligands are contemplated without departing from the scope of the invention.

As used herein, the term "Ar" or "aryl" includes five- to ten-members, preferably six- to ten-membered carbon cyclic aromatic groups, such as phenyl and naphthyl, except K. In addition to D, E or Z, the group is optionally substituted by one or more substituents selected from aryl and lower alkyl (the alkyl itself may be substituted or blocked as appropriate, as defined below ), Het, halo, cyano, nitro, OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , SR ²⁷ , C(O)SR ²⁷ or C(S)NR ²⁵ R ²⁶ , wherein R ¹⁹ to R ²⁷ each independently represent hydrogen, aryl or lower alkyl (the alkyl itself may be substituted or blocked as appropriate) , as defined below). Further, the aryl moiety may be a condensed polycyclic group such as naphthalene, a secondary biphenyl or an anthracene.

The term "metal of Group VIB or Group VIIIB" in the compound of formula I, which includes some metals such as Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Os, Ir, Pt and Pd. The metal is preferably selected from the group consisting of Ni, Pt and Pd. The metal is more preferably Pd. For the avoidance of doubt, references to Group VIB or VIIIB metals herein shall be taken to include Groups 6, 8, 9 and 10 of the Modern Periodic Table nomenclature.

As used herein, the term "Het" includes a four- to twelve-membered, preferably four- to ten-membered ring system containing one or more heteroatoms selected from the group consisting of nitrogen and oxygen. Sulfur and mixtures thereof, and the ring may contain one or more double bonds or be non-aromatic, partially aromatic or wholly aromatic in character. The ring system can be monocyclic, bicyclic or fused. Each "Het" group identified herein is optionally substituted with one or more substituents selected from the group consisting of halo, cyano, nitro, keto, and lower alkyl (the alkyl itself may be used as appropriate Substituted or capped, as defined below), OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , SR ²⁷ , C(O)SR ²⁷ or C(S)NR ²⁵ R ²⁶ , wherein R ¹⁹ to R ²⁷ each independently represent hydrogen, aryl or lower alkyl (the alkyl itself may be substituted or blocked as appropriate, as follows) Text definition). Thus, the term "Het" includes some groups, such as optionally substituted with a nitrogen tetradecyl group, a tetrahydropyrrolyl group, an imidazolyl group, a fluorenyl group, a furyl group, Azolyl, different Azolyl, Diazolyl, thiazolyl, thiadiazolyl, triazolyl, Triazolyl, thiatriazole, oxime Base, morpholinyl, pyrimidinyl, pyridyl Base, quinolyl, isoquinolyl, hexahydropyridyl, pyrazolyl and hexahydropyridyl base. Substitution on Het can be on the carbon atom of the Het ring or, where appropriate, on one or more heteroatoms.

The "Het" group can also be in the form of an N oxide.

When used herein, "lower alkyl" means a line C ₁ to C ₁₀ alkyl and includes methyl, ethyl, propyl, butyl, pentyl, hexyl group and heptyl group. Unless otherwise indicated, when sufficient carbon atoms are present, the alkyl group may be linear or branched, saturated or unsaturated, cyclic, acyclic or partially cyclic/acyclic, and/or Substituted or capped with a plurality of substituents selected from the group consisting of halo, cyano, nitro, OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , SR ²⁷ , C(O)SR ²⁷ , C(S)NR ²⁵ R ²⁶ , aryl or Het, wherein R ¹⁹ to R ²⁷ each independently represent hydrogen, aryl or low Carboxyalkyl, and/or inserted by one or more oxygen or sulfur atoms or by a decyl or dialkyl fluorenyl group.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , K, D, E and Z may be represented and the aryl group and Het may be substituted by it. a lower alkyl or alkyl group which, when present in a sufficient number of carbon atoms, may be linear or branched, saturated or unsaturated, cyclic, acyclic or partially cyclic/acyclic, and/or Or a plurality of oxygen or sulfur atoms or substituted by a decyl or dialkyl fluorenyl group, and/or substituted by one or more substituents selected from the group consisting of halo, cyano, nitro, OR ¹⁹ , OC (O R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , SR ²⁷ , C(O)SR ²⁷ , C(S)NR ²⁵ R ²⁶ Or aryl or Het, wherein each of R ¹⁹ to R ²⁷ independently represents hydrogen, aryl or lower alkyl.

Likewise, "lower alkylidene" term which A, B and J (when present) based compound represented by Formula I, when used herein, includes C ₁ lines to C ₁₀ group which It is bonded to other moiety groups at at least two positions of the group, and in other cases is defined in the same manner as "lower alkyl group".

The halogen group to which the above-mentioned group may be substituted or blocked includes a fluorine group, a chlorine group, a bromo group and an iodine group.

In the case where the compound of the formula herein contains an alkenyl group, cis (E) and trans (Z) isomerism may also occur. The present invention includes individual stereoisomers of any of the compounds of the formulae defined herein, and where appropriate, individual tautomeric forms thereof, as well as mixtures thereof. Separation of diastereomers or cis and trans isomers may be accomplished by conventional techniques, such as fractional crystallization, chromatography or by stereoisomeric mixtures of one of the formulas or their appropriate salts or derivatives. HPLC. The individual palmomers of one of the compounds of the formula may also be prepared from the corresponding optically pure intermediates, or by resolution, such as by using an appropriate pair of palmitic carriers, by HPLC of their corresponding racemates, or by Fractional crystallization of the diastereomeric salt formed by the reaction of its corresponding racemate with a suitable optically active acid or base, in a suitable manner.

All stereoisomers are included within the scope of the methods of the invention.

It will be apparent to those skilled in the art that the compound of formula I can act as a ligand which is coordinated to the Group VIB or Group VIIIB metal or compound thereof in the formation of the catalyst system of the present invention. Typically, Group VIB or Group VIIIB metals or compounds thereof are coordinated to one or more phosphorus, arsenic and/or antimony atoms of a compound of formula I.

R ¹ to R ¹⁸ preferably each independently represent a lower alkyl group or an aryl group. More preferably, R ¹ to R ¹⁸ independently represent a C ₁ to C ₆ alkyl group, a C ₁ -C ₆ alkylphenyl group (wherein the phenyl group is optionally substituted, as defined herein) or a phenyl group (wherein the phenyl group) Replaced as appropriate, as defined herein). Further preferably, R ¹ to R ¹⁸ each independently represent a C ₁ to C ₆ alkyl group, which is optionally substituted as defined herein. R ¹ to R ¹⁸ are each preferably an unsubstituted C ₁ to C ₆ alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or the third- Butyl, pentyl, hexyl and cyclohexyl.

Alternatively or additionally, each of the groups R ¹ to R ³ , R ⁴ to R ⁶ , R ⁷ to R ⁹ , R ¹⁰ to R ¹² , R ¹³ to R ¹⁵ or R ¹⁶ to R ¹⁸ may be independently formed together Ring structure, such as 1-positive Base or 1-positive Dienyl. Other examples of the composite group include a cyclic structure formed between R ^{1 -} R ¹⁸ . Alternatively, one or more of these groups may represent the solid phase to which the ligand is attached.

In a particularly preferred embodiment of the invention, R ¹ , R ⁴ , R ⁷ , R ¹⁰ , R ¹³ and R ¹⁶ each represent the same lower alkyl, aryl or Het moiety, as herein Definitions, R ² , R ⁵ , R ⁸ , R ¹¹ , R ¹⁴ and R ¹⁷ each represent the same lower alkyl, aryl or Het moiety, as defined herein, and R ³ , R ⁶ , R ⁹ R ¹² , R ¹⁵ and R ¹⁸ each represent the same lower alkyl, aryl or Het moiety as defined herein. R ¹ , R ⁴ , R ⁷ , R ¹⁰ , R ¹³ and R ¹⁶ each preferably represent the same C ₁ -C ₆ alkyl group, especially an unsubstituted C ₁ -C ₆ alkyl group, such as a methyl group. Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl or cyclohexyl; R ² , R ⁵ , R ⁸ , R ¹¹ , R ¹⁴ and R ¹⁷ each independently represents the same C ₁ -C ₆ alkyl group, as defined above; and R ³ , R ⁶ , R ⁹ , R ¹² , R ¹⁵ and R ¹⁸ each independently represent the same C ₁ -C ₆ alkyl group, As defined above. For example: R ¹ , R ⁴ , R ⁷ , R ¹⁰ , R ¹³ and R ¹⁶ each represent a methyl group; R ² , R ⁵ , R ⁸ , R ¹¹ , R ¹⁴ and R ¹⁷ each represent an ethyl group; and R ³ , R ⁶ , R ⁹ , R ¹² , R ¹⁵ and R ¹⁸ each represent n-butyl or n-pentyl.

In a particularly preferred embodiment of the invention, each of the R ¹ to R ¹⁸ groups represents the same lower alkyl, aryl or Het moiety, as defined herein. Each of R ¹ to R ¹⁸ preferably denotes the same C ₁ to C ₆ alkyl group, particularly an unsubstituted C ₁ -C ₆ alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-Butyl, isobutyl, tert-butyl, pentyl, hexyl and cyclohexyl. Each of R ¹ to R ¹⁸ preferably represents a methyl group.

In the compounds of formula I, each of Q ¹ , Q ² and Q ³ (when present) is preferably the same. Each of Q ¹ , Q ² and Q ³ (when present) preferably represents phosphorus.

In the compounds of formula I, A, B and J (when present) each independently represents a preferred system a C ₁ to C ₆ alkylidene, optionally substituted lines which, as defined herein, for example, lower alkyl. The lower alkylene group represented by A, B and J (when present) is preferably unsubstituted. The particularly preferred lower alkylene group which A, B and J can independently represent is -CH ₂ - or -C ₂ H ₄ -. Each of A, B and J (when present) represent the same line of best times lower alkyl group, as defined herein, particularly -CH ₂ -.

In the compound of formula I, when K, D, E or Z does not represent -J-Q ³ (CR ¹³ (R ¹⁴ )(R ¹⁵ ))CR ¹⁶ (R ¹⁷ )(R ¹⁸ ), K, D, E Or Z preferably represents hydrogen, lower alkyl, phenyl or lower alkylphenyl. More preferably, K, D, E or Z means hydrogen, phenyl, C ₁ -C ₆ alkylphenyl or C ₁ -C ₆ alkyl, such as methyl, ethyl, propyl, butyl, pentyl and Heji. The K, D, E or Z best means hydrogen.

In the compound of formula I, when K, D, E and Z together with the carbon atom of the aryl ring to which they are attached do not form a benzene ring, K, D, E and Z preferably each independently represent hydrogen and are low. Carboalkyl, phenyl or lower alkylphenyl. More preferably, each of K, D, E and Z independently represents hydrogen, phenyl, C ₁ -C ₆ alkylphenyl or C ₁ -C ₆ alkyl, such as methyl, ethyl, propyl, butyl, pentyl Base and hexyl. More preferably, K, D, E and Z represent the same substituent. The best system is hydrogen.

In the compound of formula I, when K, D, E or Z does not represent -J-Q ³ (CR ¹³ (R ¹⁴ )(R ¹⁵ ))CR ¹⁶ (R ¹⁷ )(R ¹⁸ ), and K, D, E And when Z and the carbon atoms of the aryl ring to which they are attached do not form a benzene ring, each of K, D, E and Z preferably represents the same group and is selected from hydrogen, lower alkyl, aryl or het, as defined herein; in particular hydrogen or C ₁ -C ₆ alkyl (more particularly unsubstituted of C ₁ -C ₆ alkyl), especially hydrogen.

In the compound of formula I, when two of K, D, E and Z together with the carbon atom of the aryl ring to which they are attached form a benzene ring, the phenyl ring is preferably substituted by one or more Substituent, the substituent is selected from aryl, lower alkyl (the alkyl itself may be optionally substituted or blocked, as defined below), Het, halo, cyano, nitro, OR ¹⁹ , OC(O) R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , SR ²⁷ , C(O)SR ²⁷ or C(S)NR ²⁵ R ²⁶ , Wherein R ¹⁹ to R ²⁷ each independently represent hydrogen or lower alkyl (the alkyl group itself may be optionally substituted or blocked, as defined herein). More preferably, the benzene ring is not substituted by any substituent, that is, it has only a hydrogen atom.

Preferred compounds of formula I include the following compounds wherein: A and B each independently represent an unsubstituted C ₁ to C ₆ alkyl group; K, D, Z and E each independently represent hydrogen, C ₁ -C ₆ alkyl, Phenyl, C ₁ -C ₆ alkylphenyl or -J-Q ³ (CR ¹³ (R ¹⁴ )(R ¹⁵ ))CR ¹⁶ (R ¹⁷ )(R ¹⁸ ), wherein J represents unsubstituted C ₁ To a C ₆ alkyl group; or two of K, D, Z and E together with the carbon atom of the aryl ring to which they are attached form a benzene ring, which is optionally selected from the group consisting of lower alkane Substituted by a substituent of a phenyl group or a lower alkylphenyl group.

R ¹ to R ¹⁸ each independently represent a C ₁ to C ₆ alkyl group, a phenyl group or a C ₁ to C ₆ alkylphenyl group.

Further preferred compounds of formula I include the following compounds wherein: both A and B represent -CH ₂ - or C ₂ H ₄ , especially CH ₂ ; K, D, Z and E each independently represent hydrogen, C ₁ -C _{a 6} alkylphenyl group or a C ₁ -C ₆ alkyl group or a -J-Q ³ (CR ¹³ (R ¹⁴ )(R ¹⁵ ))CR ¹⁶ (R ¹⁷ )(R ¹⁸ ), wherein the J system is the same as A; Two of K, D, E and Z together with the carbon atom of the aryl ring to which they are attached form an unsubstituted benzene ring; R ¹ to R ¹⁸ each independently represent a C ₁ to C ₆ alkyl group; Preferred compounds of formula I include the following compounds wherein: R ¹ to R ¹⁸ are the same and each represents a C ₁ to C ₆ alkyl group, especially a methyl group.

Still further preferred compounds of Formula I include compounds wherein: K, D, Z and E are each independently selected from the group consisting of hydrogen or a C ₁ to C ₆ alkyl, particularly where each of K, D, Z and E represent the same group , in particular, wherein each of K, D, Z and E represents hydrogen; or K represents -CH ₂ -Q ³ (CR ¹³ (R ¹⁴ )(R ¹⁵ ))CR ¹⁶ (R ¹⁷ )(R ¹⁸ ), and D, Z and E are each independently selected from hydrogen or a C ₁ to C ₆ alkyl group, particularly wherein both D and E represent the same group, especially wherein D, Z and E represent hydrogen.

Particularly preferred compounds of formula I include the following compounds wherein: each of R ¹ to R ¹² is the same and represents a methyl group; A and B are the same and represent -CH ₂ -; K, D, Z and E are the same, And represents hydrogen.

In still further embodiments, at least one (CR ^x R ^y R ^z ) group is attached to Q ¹ and/or Q ² , meaning CR ¹ R ² R ³ , CR ⁴ R ⁵ R ⁶ , CR ⁷ R ⁸ R ⁹ or CR ¹⁰ R ¹¹ R ¹² , which may alternatively be represented by a group (Ad), wherein: Ad each independently represents optionally substituted gold steel alkyl or emblem alkyl, via its tertiary carbon atom Any one of which is bonded to a phosphorus atom selected from one or more substituents selected from the group consisting of hydrogen, lower alkyl, halo, cyano, nitro, OR ¹⁹ , OC(O)R ²⁰ , C ( O) R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , C(S)R ²⁵ R ²⁶ , SR ²⁷ or C(O)SR ²⁷ ; Two (CR ^x R ^y R ^z ) groups of one or two Q ¹ and/or Q ² or Q ³ (if present) form an optionally substituted 2-phosphorus tricyclic [3.3.1.1{ 3,7}] fluorenyl (also known as 2-phosphorus-gold steel alkyl (2-PA-group)) or a derivative thereof, as defined more particularly below, or a ring system of the formula Wherein R ⁴⁹ and R ⁵⁴ each independently represent hydrogen, lower alkyl or aryl; R ⁵⁰ to R ⁵³ , when present, each independently represent hydrogen, lower alkyl, aryl or Het; and Y represents oxygen, sulfur Or N-R ⁵⁵ ; and R ⁵⁵ , when present, means hydrogen, lower alkyl or aryl.

In this particular embodiment, Formula I can be expressed as: (Ad) _S (CR ⁷ R ⁸ R ⁹ ) _T Q ² -A-(K,D)Ar(E,Z)-B-Q ¹ ( Ad) _U (CR ¹ R ² R ³ ) _V wherein Ar, A, B, K, D, E and Z, Q ¹ , Q ² and Q ³ , and R ¹ to R ²⁷ are as defined above, except K, D, E and Z may represent -J-Q ³ (Ad) _W (CR ¹³ (R ¹⁴ )(R ¹⁵ ) _X instead of -J-Q ³ (CR ¹³ (R ¹⁴ )(R ¹⁵ ))CR ¹⁶ ( R ¹⁷ )(R ¹⁸ ), and Ad is as defined above, S & U=0, 1 or 2, with the condition that S+U≧1; T & V=0, 1 or 2, with the condition that T+V≦3; & X=0, 1 or 2.

In addition to the preferred embodiments of R ¹ to R ¹⁸ , Q ¹ to Q ³ , A, B, J (when present), K, D, E or Z, R ¹⁹ to R ²⁷ as indicated above, All are equally applicable to specific embodiments of the invention in which at least one (Ad) group is present, the following also applies.

Further preferred compounds of formula I include the compounds wherein: A and B both represent -CH ₂ - or -C ₂ H ₄ -, especially -CH ₂ -; K, D, Z and E each independently represent hydrogen, C ₁ -C ₆ alkylphenyl or C ₁ -C ₆ alkyl or -J-Q ³ (Ad) _W (CR ¹³ (R ¹⁴ )(R ¹⁵ )) _X , wherein the J system is the same as A; or K And two of D, E and Z together with the carbon atom of the aryl ring to which they are attached form an unsubstituted benzene ring; R ¹ to R ³ , R ⁷ to R ⁹ and R ¹³ to R ¹⁵ (when When present, each independently represents a C ₁ to C ₆ alkyl group, and the total number of (Ad) groups attached to Q ¹ and Q ² is ≧3, meaning S+U≧3, and W and X=0, 1 or 2 .

Still further preferred compounds of formula I include those wherein R ¹ to R ³ , R ⁷ to R ⁹ and R ¹³ to R ¹⁵ (when present) are the same and each represents a C ₁ to C ₆ alkyl group, particularly It is a methyl group, and the total number of (Ad) groups attached to Q ¹ and Q ² is ≧3, which means S+U≧3.

Still further preferred compounds of Formula I include compounds wherein: K, D, Z and E are each independently selected from the group consisting of hydrogen or a C ₁ to C ₆ alkyl, particularly where each of K, D, Z and E represent the same group , in particular, wherein each of K, D, Z and E represents hydrogen; or K represents -CH ₂ -Q ³ (Ad) _W (CR ¹³ (R ¹⁴ )(R ¹⁵ ) _X , and D, Z and E are each independently selected from the group consisting of hydrogen or a C ₁ to C ₆ alkyl, particularly where both D and E represent the same group, especially where D, Z and E represent hydrogen, wherein W and X = 0,1 or 2.

Particularly preferred compounds of formula I include the following compounds wherein each R ¹ to R ³ is the same as R ⁷ to R ⁹ and represents a methyl group or an (Ad) group attached to Q ¹ and Q ² The total number is 2, meaning that S+U=2; A and B are the same, and represent -CH ₂ -; K, D, Z and E are the same and represent hydrogen.

Plus the particular compound of formula I include the following compounds, wherein the Ad-based, bonded to the same position on Q ₁ or Q ₂ in each case. Preferably, S≧1, and U≧1, more preferably, S=2, and U≧1, or vice versa, the best case is, S & U=2, where S is connected to Q ² The number of (Ad) groups, and U is the number of (Ad) groups attached to Q ¹ .

Specific, but non-limiting examples of bidentate ligands in this particular embodiment include the following: 1,2 bis(di-gold-steel alkylphosphinomethyl)benzene, 1,2 bis (di-3) , 5-dimethyl fund steel alkyl phosphinomethyl) benzene, 1,2 bis (di-5-third-butane fund steel alkylphosphinomethyl) benzene, 1,2 bis (1-gold lanthanane Tris-butyl-phosphinomethyl)benzene, 1-(di-gold-steel alkylphosphinomethyl)-2-(di-tertiary-butylphosphinomethyl)benzene, 1-(di- Tertiary-butylphosphinomethyl)-2-(di-captoalkylphosphinomethyl)benzene, 1-(di-t-butylphosphinomethyl)-2-(phosphorus-gold steel alkyl -P-methyl)benzene, 1-(di-gold-steel alkylphosphinomethyl)-2-(phosphorus-gold steel alkyl-P-methyl)benzene, 1-(third-butane fund steel alkyl Phosphylmethyl)-2-(di-gold steel alkylphosphinomethyl)benzene and 1-[(P-(2,2,6,6,-tetra-methylphosphan-4-one)phosphine Methyl)]-2-(phosphorus-gold steel alkyl-P-methyl)benzene, wherein "phosphorus-gold steel alkyl" is selected from 2-phosphorus-1,3,5,7-tetramethyl -6,9,10-trioxy gold steel alkyl, 2-phosphorus-1,3,5-trimethyl-6,9,10 trioxy gold steel alkyl, 2-phosphorus-1,3,5,7-tetrakis(trifluoromethyl)-6,9,10-trioxy gold steel alkyl or 2-phospho-1,3,5-tris(trifluoromethyl) -6,9,10-trioxy gold steel alkyl. Nonetheless, it will be apparent to those skilled in the art that other bidentate ligands are contemplated without departing from the scope of the invention.

As mentioned herein, in yet another specific embodiment, the bidentate phosphine coordination system has the general formula (II) Wherein: A ₁ and A ₂ , and A ₃ , A ₄ and A ₅ (when present) each independently represent a lower carbene alkyl group; K ¹ is selected from the group consisting of hydrogen, lower alkyl, aryl, Het, Halo, cyano, nitro, -OR ¹⁹ , -OC(O)R ²⁰ , -C(O)R ²¹ , -C(O)OR ²² , -N(R ²³ )R ²⁴ , -C(O N(R ²⁵ )R ²⁶ , -C(S)(R ²⁷ )R ²⁸ , -SR ²⁹ , -C(O)SR ³⁰ , -CF ₃ or -A ₃ -Q ³ (X ⁵ )X ⁶ ; D ¹ is selected from the group consisting of hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, -OR ¹⁹ , -OC(O)R ²⁰ , -C(O)R ²¹ , -C( O) OR ²² , -N(R ²³ )R ²⁴ , -C(O)N(R ²⁵ )R ²⁶ , -C(S)(R ²⁷ )R ²⁸ , -SR ²⁹ , -C(O)SR ³⁰ , -CF ₃ or -A ₄ -Q ⁴ (X ⁷ )X ⁸ ; E ¹ is selected from the group consisting of hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, -OR ¹⁹ , - OC(O)R ²⁰ , -C(O)R ²¹ , -C(O)OR ²² , -N(R ²³ )R ²⁴ , -C(O)N(R ²⁵ )R ²⁶ , -C(S) (R ²⁷ )R ²⁸ , -SR ²⁹ , -C(O)SR ³⁰ , -CF ₃ or -A ₅ -Q ⁵ (X ⁹ )X ¹⁰ ; or both D ¹ and E ¹ and their The carbon atoms of the cyclopentadienyl ring are formed together as appropriate The phenyl ring: X ¹ represents ^{CR 1 (R 2) (R} 3), emblem or adamantyl group, X ² represents a ^{CR 4 (R 5) (R} 6), alkyl or adamantyl emblem, Or X ¹ and X ² together with the Q ² to which they are attached form an optionally substituted 2-phosphorus tricyclo[3.3.1.1{3,7}]fluorenyl or a derivative thereof, or X ¹ and X ² Together with their connected Q ² to form a ring system of formula IIIa X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), an emblem alkyl or a gold alkyl group, and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), an emblem alkyl or a gold alkyl group, or R ³ and X ⁴ and the Q ¹ to which they are attached together form an optionally substituted 2-phosphorus tricyclo[3.3.1.1{3,7}]mercapto group or a derivative thereof, or X ³ and X ⁴ and their The connected Q ¹ together form the ring system of the formula IIIb X ⁵ represents CR ¹³ (R ¹⁴ )(R ¹⁵ ), an emblem alkyl or a gold alkyl group, and X ⁶ represents CR ¹⁶ (R ¹⁷ )(R ¹⁸ ), an emblem alkyl or a gold alkyl group, or X ⁵ and X ⁶ and the Q ³ to which they are attached together form an optionally substituted 2-phosphorus tris[3.3.1.1{3,7}]fluorenyl or a derivative thereof, or X ⁵ and X ⁶ and their The connected Q ³ together form the ring system of the formula IIIc X ⁷ represents CR ³¹ (R ³² )(R ³³ ), an emblem alkyl or a gold alkyl group, and X ⁸ represents CR ³⁴ (R ³⁵ ) (R ³⁶ ), an emblem alkyl or a gold alkyl group, or X ⁷ and X ⁸ and the Q ⁴ to which they are attached together form an optionally substituted 2-phosphorus tricyclo[3.3.1.1{3,7}] fluorenyl group or a derivative thereof, or X ⁷ and X ⁸ and their Connected Q ⁴ together to form a ring system of formula IIId X ⁹ represents CR ³⁷ (R ³⁸ ) (R ³⁹ ), an emblem alkyl or a gold alkyl group, and X ¹⁰ represents CR ⁴⁰ (R ⁴¹ ) (R ⁴² ), an emblem alkyl or a gold alkyl group, or X ⁹ and X ¹⁰ together with the Q ⁵ to which they are attached form an optionally substituted 2-phosphorus tris[3.3.1.1.{3,7}] fluorenyl group or a derivative thereof, or X ⁹ and X ¹⁰ and their The connected Q ⁵ together form a ring system of formula IIIe And in still further embodiments, Q ¹ and Q ² and Q ³ , Q ⁴ and Q ⁵ (when present) each independently represent phosphorus, arsenic or antimony; M represents a Group VIB or VIIIB metal or a metal cation thereof ; L ₁ represents optionally substituted cyclopentadienyl, indenyl or aryl; L ₂ represents one or more ligands, each of which is independently selected from hydrogen, lower alkyl, alkylaryl , halo, CO, P(R ⁴³ )(R ⁴⁴ )R ⁴⁵ or N(R ⁴⁶ )(R ⁴⁷ )R ⁴⁸ ; R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, each independently represent hydrogen , lower alkyl, aryl, halo or Het; R ¹⁹ to R ³⁰ and R ⁴³ to R ⁴⁸ , when present, each independently represent hydrogen, lower alkyl, aryl or Het; R ⁴⁹ , R ⁵⁴ And R ⁵⁵ , when present, each independently represent hydrogen, lower alkyl or aryl; R ⁵⁰ to R ⁵³ , when present, each independently represent hydrogen, lower alkyl, aryl or Het; Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ , when present, each independently represents oxygen, sulfur or N-R ⁵⁵ ; n = 0 or 1; and m = 0 to 5; provided that when n = 1, Then m is equal to 0, and when n is equal to 0, then m is not equal to 0.

In the compound of formula II, when K ¹ represents -A ₃ -Q ³ (X ⁵ )X ⁶ and E ¹ represents -A ₅ -Q ⁵ (X ⁹ )X ¹⁰ , then D ¹ preferably represents -A ₄ -Q ⁴ (X ⁷ )X ⁸ .

In this particular embodiment, R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, preferably each independently represent hydrogen, optionally substituted C ₁ to C ₆ alkyl, C ₁ -C ₆ Alkylphenyl (wherein phenyl is optionally substituted, as defined herein), trifluoromethyl or phenyl (wherein phenyl is optionally substituted, as defined herein). R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, more preferably each independently represent hydrogen, C ₁ to C ₆ alkyl, which is optionally substituted, as defined herein, trifluoromethyl or as defined herein. A substituted phenyl group. R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, more preferably each independently represent hydrogen, unsubstituted C ₁ to C ₆ alkyl, or phenyl, which is optionally one or more Substituted by a substituent, the substituent is selected from unsubstituted C ₁ to C ₆ alkyl or OR ¹⁹ , wherein R ¹⁹ represents hydrogen or an unsubstituted C ₁ to C ₆ alkyl group. R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, more preferably independently represent hydrogen, or unsubstituted C ₁ to C ₆ alkyl, such as methyl, ethyl, n-propyl, iso Propyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl and cyclohexyl, especially methyl. R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, each independently represents an unsubstituted C ₁ to C ₆ alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-Butyl, isobutyl, tert-butyl, pentyl, hexyl and cyclohexyl, especially methyl.

Alternatively or additionally, one or more of the groups R ¹ to R ³ , R ⁴ to R ⁶ , R ⁷ to R ⁹ , R ¹⁰ to R ¹² , R ¹³ to R ¹⁵ , R ¹⁶ to R ¹⁸ , R ³¹ to R ³³ , R ³⁴ to R ³⁶ , R ³⁷ to R ³⁹ or R ⁴⁰ to R ⁴² (when present) together with the carbon atoms to which they are attached may independently form a cyclic alkyl structure, such as 1-positive Base or 1-positive Dienyl.

Alternatively or additionally, one or more of the groups R ¹ and R ² , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ¹⁰ and R ¹¹ , R ¹³ and R ¹⁴ , R ¹⁶ and R ¹⁷ , R ³¹ and R ³² , R ³⁴ and R ³⁵ , R ³⁷ and R ³⁸ or R ⁴⁰ and R ⁴¹ (when present) together with the carbon atom to which they are attached may independently form a cyclic alkyl structure, preferably C ₅ to C. _a cyclic alkyl structure such as cyclohexyl and cyclopentyl, and R ³ , R ⁶ , R ⁹ , R ¹² , R ¹⁵ , R ¹⁸ , R ³³ , R ³⁶ , R ³⁹ and R ⁴² (when present) Each independently represents hydrogen, lower alkyl, trifluoromethyl or aryl, as defined above, especially unsubstituted C ₁ to C ₆ alkyl and hydrogen, especially unsubstituted C ₁ to C ₆ alkane base.

In a particularly preferred embodiment, each of R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, does not represent hydrogen. Suitably, such an arrangement means that Q ¹ , Q ² , Q ³ , Q ⁴ and Q ^{5 are} bonded individually to the carbon atoms of X ¹ to X ¹⁰ which do not carry a hydrogen atom.

Preferably, R ¹ , R ⁴ , R ⁷ , R ¹⁰ , R ¹³ , R ¹⁶ , R ³¹ , R ³⁴ , R ³⁷ and R ⁴⁰ (when present) each represent the same substituent, as defined herein; R ² , R ⁵ , R ⁸ , R ¹¹ , R ¹⁴ , R ¹⁷ , R ³² , R ³⁵ , R ³⁸ and R ⁴¹ (when present) each represent the same substituent, as defined herein; and R ³ , R ⁶ , R ⁹ , R ¹² , R ¹⁵ , R ¹⁸ , R ³³ , R ³⁶ , R ³⁹ and R ⁴² (when present) each represent the same substituent, as defined herein.

R ¹ , R ⁴ , R ⁷ , R ¹⁰ , R ¹³ , R ¹⁶ , R ³¹ , R ³⁴ , R ³⁷ and R ⁴⁰ (when present) preferably each represent the same C ₁ -C ₆ alkyl group, particularly Is an unsubstituted C ₁ -C ₆ alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl or cyclic Hexyl or trifluoromethyl; R ² , R ⁵ , R ⁸ , R ¹¹ , R ¹⁴ , R ¹⁷ , R ³² , R ³⁵ , R ³⁸ and R ⁴¹ (when present) each independently represent the same C ₁ -C _{a 6} alkyl group, as defined above, or a trifluoromethyl group; and R ³ , R ⁶ , R ⁹ , R ¹² , R ¹⁵ , R ¹⁸ , R ³³ , R ³⁶ , R ³⁹ and R ⁴² (when present) Independently represents the same C ₁ -C ₆ alkyl group, as defined above, or trifluoromethyl. For example: R ¹ , R ⁴ , R ⁷ , R ¹⁰ , R ¹³ and R ¹⁶ (when present) each represent a methyl group; R ² , R ⁵ , R ⁸ , R ¹¹ , R ¹⁴ and R ¹⁷ each represent an ethyl group. (when present); and R ³ , R ⁶ , R ⁹ , R ¹² , R ¹⁵ and R ¹⁸ (when present) each represent n-butyl or n-pentyl.

In a particularly preferred embodiment, each of R ¹ to R ¹⁸ and R ³¹ to R ⁴² (when present) represents the same substituent, as defined herein. Each of R ¹ to R ¹⁸ and R ³¹ to R ⁴² preferably denotes the same C ₁ to C ₆ alkyl group, particularly an unsubstituted C ₁ -C ₆ alkyl group such as methyl, ethyl, or -propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl and cyclohexyl, or trifluoromethyl. Each of the R ¹ to R ¹⁸ and R ³¹ to R ⁴² groups preferably represents an unsubstituted C ₁ -C ₆ alkyl group, particularly a methyl group.

As used herein, the term "gold steel alkyl" means a gold steel alkyl group which can be individually bonded to Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ at position 1 or 2. The tricyclic [3.3.1.1.{3,7}] fluorenyl group is the system name of the gold steel alkyl group. Suitably, Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ may be individually combined to one or two One or two positions of the three rings [3.3.1.1.{3,7}]. Q ¹ and Q ² and Q ³ , Q ⁴ and Q ⁵ , when present, are preferably bonded to the tertiary carbon of one or more gold steel alkyl groups. Suitably, when the gold alkyl group represents an unsubstituted gold steel alkyl group, Q ¹ and Q ² and Q ³ , Q ⁴ and Q ⁵ (when present) are preferably bonded to one or more tricyclic rings. And [3.3.1.1{3,7}] 1 position of the sulfhydryl group, meaning that the carbon atom of the gold steel alkyl group does not have a hydrogen atom.

In addition to a hydrogen atom, the gold alkyl group may optionally contain one or more substituents selected from the group consisting of lower alkyl, -OR ¹⁹ , -OC(O)R ²⁰ , halo, nitro, -C(O). R ²¹ , -C(O)OR ²² , cyano, aryl, -N(R ²³ )R ²⁴ , -C(O)N(R ²⁵ )R ²⁶ , -C(S)(R ²⁷ )R ²⁸ , -CF ₃ , -P(R ⁵⁶ )R ⁵⁷ , -PO(R ⁵⁸ )(R ⁵⁹ ), -PO ₃ H ₂ , -PO(OR ⁶⁰ )(OR ⁶¹ ) or -SO ₃ R ⁶² , wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , lower alkyl, cyano and aryl are as defined herein, and R ⁵⁶ to R ⁶² Each independently represents hydrogen, lower alkyl, aryl or Het.

Suitably, when the gold alkyl group is substituted by one or more substituents as defined above, highly preferred substituents include unsubstituted C ₁ to C ₈ alkyl, -OR ¹⁹ , -OC(O)R ²⁰ , phenyl, -C(O)OR ²² , fluoro, -SO ₃ H, -N(R ²³ )R ²⁴ , -P(R ⁵⁶ )R ⁵⁷ , -C(O)N(R ²⁵ )R ²⁶ and -PO(R ⁵⁸ )(R ⁵⁹ ), -CF ₃ , wherein R ¹⁹ represents hydrogen, unsubstituted C ₁ -C ₈ alkyl or phenyl, R ²⁰ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represent hydrogen or an unsubstituted C ₁ -C ₈ alkyl group, and R ⁵⁶ to R ⁵³ and R ⁵⁶ each independently represent an unsubstituted C ₁ -C ₈ alkyl group or a phenyl group.

Suitably, in addition to a hydrogen atom, the gold alkyl group may comprise up to 10 substituents as defined above, preferably up to 5 substituents as defined above, more preferably up to 3 substituents as defined above . Suitably, in addition to a hydrogen atom, when the gold steel alkyl group comprises one or more substituents as defined herein, each substituent is preferably the same. Preferred substituents are unsubstituted C ₁ -C ₈ alkyl and trifluoromethyl, especially unsubstituted C ₁ -C ₈ alkyl, such as methyl. A highly preferred gold steel alkyl group contains only hydrogen atoms, meaning that the gold steel alkyl group is unsubstituted.

When more than one gold steel alkyl group is present in the compound of formula III, each of the gold steel alkyl groups is preferably the same.

The term "2-phosphorus tricyclic" [3.3.1.1.{3,7}] thiol, which means the formation of X ¹ and X ² together with the combination of Q ² to which they are attached Phosphorus-gold steel alkyl, a 2-phosphorus-gold steel alkyl group formed by the combination of X ³ and X ⁴ with the Q ¹ to which they are attached, by which X ⁵ and X ⁶ are attached a 2-phosphorus-gold steel alkyl group formed by a combination of Q ³ , a 2-phosphorus-gold steel alkyl group formed by a combination of X ⁷ and X ⁸ with the Q ⁴ to which they are attached, and by a 2-phosphorus-gold steel alkyl group formed by the combination of X ⁹ and X ¹⁰ and the Q ^{5 to which} they are attached, wherein Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ are in the gold alkyl group 2 - Position, wherein the system forms an integral part, and each of Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ represents phosphorus.

In addition to a hydrogen atom, a 2-phosphorodicyclo[3.3.1.1.{3,7}]fluorenyl group (referred to herein as a 2-phosphorus-gold steel alkyl group) may optionally contain one or more substituents. Suitable substituents include those as defined herein with respect to the gold alkyl group. Highly preferred substituents include lower alkyl, especially unsubstituted C ₁ -C ₈ alkyl, especially methyl, trifluoromethyl, -OR ¹⁹ , wherein R ¹⁹ is as defined herein, especially Substituted C ₁ -C ₈ alkyl or aryl, and 4-dodecylphenyl. When the 2-phosphorus-gold steel alkyl group contains more than one substituent, each substituent is preferably the same.

The 2-phosphorus-gold steel alkyl group is preferably attached to one or more of the 1, 3, 5 or 7 positions, and is substituted with a substituent as defined herein. The 2-phosphorus-gold steel alkyl group is more preferably substituted at each of the 1, 3 and 5 positions. Suitably, such an arrangement means a phosphorus atom of a 2-phosphorus-gold steel alkyl group bonded to a carbon atom in a gold steel alkyl skeleton having no hydrogen atom. The 2-phosphorus-gold steel alkyl group is substituted at each of the 1, 3, 5 and 7 positions. When the 2-phosphorus-gold steel alkyl group contains more than one substituent, each substituent is preferably the same. Particularly preferred substituents are unsubstituted C ₁ -C ₈ alkyl and trifluoromethyl, especially unsubstituted C ₁ -C ₈ alkyl, such as methyl.

The 2-phosphorus-gold steel alkyl group preferably contains a hetero atom other than the 2-phosphorus atom in the 2-phosphorus-gold steel alkyl skeleton. Suitable other heteroatoms include oxygen and sulfur atoms, especially oxygen atoms. More preferably, the 2-phosphorus-gold steel alkyl group contains one or more other heteroatoms at the 6, 9 and 10 positions. More preferably, the 2-phosphorus-gold steel alkyl group contains another hetero atom at each of the 6, 9 and 10 positions. When the 2-phosphorus-gold steel alkyl group contains two or more other hetero atoms in the 2-phosphorus-gold steel alkyl skeleton, each of the other hetero atoms is preferably the same. Particularly preferred is a 2-phosphorus-gold steel alkyl group which may optionally be substituted by one or more substituents as defined herein, which are included at positions 6, 9 and 10 of the 2-phosphorus-gold steel alkyl skeleton. Oxygen atom.

A highly preferred 2-phosphorus-gold steel alkyl group as defined herein includes 2-phosphorus-1,3,5,7-tetramethyl-6,9,10-trioxy gold steel alkyl, 2-phosphorus-1 ,3,5-trimethyl-6,9,10-trioxy gold steel alkyl, 2-phosphorus-1,3,5,7-tetrakis(trifluoromethyl)-6,9,10-trioxane Gold steel alkyl and 2-phosphorus-1,3,5-tris(trifluoromethyl)-6,9,10-trioxy gold steel alkyl. The 2-phosphorus-gold steel alkyl group is preferably selected from the group consisting of 2-phosphorus-1,3,5,7-tetramethyl-6,9,10-trioxy gold steel alkyl or 2-phosphorus-1,3. 5,-Trimethyl-6,9,10-trioxy gold steel alkyl.

When more than one 2-phosphorus-gold steel alkyl group is present in the compound of formula III, each 2-phosphorus-gold steel alkyl group is preferably the same.

The above definition of the term "2-phosphoro-tricyclo[3.3.1.1.{3,7}]thiol" applies equally to when this group is present in formula I, but where is in formula III X ⁿ , meaning X ¹ , X ² , X ³ ... X ¹⁰ , represents CR ^x R ^y R ^z in formula I, meaning CR ¹ R ² R ³ ,...CR ¹⁶ R ¹⁷ R ¹⁸ .

As used herein, the term emblem alkyl means an emblem alkyl (also known as di-gold alkyl) which can be individually bonded to Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ . Q ¹ and Q ² and Q ³ , Q ⁴ and Q ⁵ , when present, are preferably bonded to one of the tertiary carbon atoms of the alkylene group. Suitably, when the emblem alkyl is unsubstituted, Q ¹ and Q ² and Q ³ , Q ⁴ and Q ⁵ (when present) are preferably bonded to the 1-position of one or more of the emblem alkyl groups.

In addition to a hydrogen atom, the emblem alkyl group may optionally contain one or more substituents. Suitable substituents include the substituents as defined herein with respect to the gold alkyl group. Highly preferred substituents include unsubstituted C ₁ -C ₆ alkyl groups, especially methyl groups, and trifluoromethyl groups. The emblem alkyl is preferably unsubstituted and contains only hydrogen atoms.

When more than one emblem alkyl group is present in the compound of formula III, each of the emblem alkyl groups is preferably the same.

In the case where one or more ring systems of formula IIIa, IIIb, IIIc, IIId or IIIe are present in the compound of formula III, R ⁵⁰ to R ⁵³ preferably each independently represent lower alkyl, aryl or Het, The group is substituted and/or capped as appropriate, as defined herein. Such an arrangement means that Q ² , Q ¹ , Q ³ , Q ⁴ and Q ⁵ of the ring system of formulae IIIa to IIIe are not individually bonded to a carbon atom bearing a hydrogen atom. Further preferably, R ⁵⁰ to R ⁵³ independently represent a C ₁ -C ₆ alkyl group which is optionally substituted, preferably an unsubstituted C ₁ -C ₆ alkyl group, optionally unsubstituted C ₁ - a C ₆ alkyl substituted phenyl group, or OR ¹⁹ , wherein R ¹⁹ represents an unsubstituted C ₁ -C ₆ alkyl group, or a trifluoromethyl group. ^More preferably, R ⁵⁰ to R ⁵³ each represent the same group as defined herein, especially an unsubstituted C ₁ -C ₆ alkyl group, especially a methyl group.

In the case where one or more of the ring systems of formulae IIIa to IIIe are present in the compound of formula III, R ⁴⁹ and R ^{54 are} preferably each independently represented as optionally substituted C ₁ -C ₆ alkyl, preferably un. a substituted C ₁ -C ₆ alkyl group, optionally substituted by a C ₁ -C ₆ alkyl group, or OR ¹⁹ , wherein R ¹⁹ represents an unsubstituted C ₁ -C ₆ alkyl group, Trifluoromethyl or hydrogen. More preferably, R ⁴⁹ and R ⁵⁴ represent the same groups as defined herein, especially hydrogen.

In the case where one or more of the ring systems of the formulae IIIa to IIIe are present in the compound of the formula III, Y ¹ to Y ^{5 are} preferably the same. Each of Y ¹ to Y ⁵ preferably represents oxygen. Where more than one ring system of formulae IIIa to IIIe is present in the compound of formula III, each such ring system is preferably identical.

Preferred embodiments of the invention include the following, wherein X ¹ represents CR ¹ (R ² )(R ³ ), X ² represents CR ⁴ (R ⁵ )(R ⁶ ), and X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ), and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ); X ¹ represents CR ¹ (R ² )(R ³ ), X ² represents a gold steel alkyl group, and X ³ represents CR ⁷ (R ^{8 )} (R ⁹ ), and X ⁴ represents a gold steel alkyl group; X ¹ represents CR ¹ (R ² )(R ³ ), X ² represents an emblem alkyl group, and X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), And X ⁴ represents an emblem alkyl; X ¹ represents CR ¹ (R ² )(R ³ ), X ² represents CR ⁴ (R ⁵ )(R ⁶ ), and X ³ and X ⁴ and the Q ^{1 to which} they are attached Together form a ring system of formula IIIb or a 2-phosphorus-gold steel alkyl group; X ¹ represents CR ¹ (R ² )(R ³ ), X ² represents a gold steel alkyl group, X ³ and X ⁴ are linked to them. Q ¹ together form a ring system of formula IIIb or a 2-phosphorus-gold steel alkyl group; X ¹ represents CR ¹ (R ² )(R ³ ), X ² represents an emblemic alkyl group, and X ³ is bonded to X ⁴ and to them. Q ¹ together form a ring system of formula IIIb or a 2-phosphorus-gold steel alkyl group; X ¹ to X ⁴ each independently represent a gold steel alkyl group; X ¹ to X ⁴ each independently represent an emblemic alkyl group; X ¹ and X ² Each independently represents a gold alkyl group, and each of X ³ and X ⁴ independently represents an emblem alkyl group; X ¹ and X ³ are independently represented by a gold steel alkyl group, and X ² and X ⁴ are independently represented by an emblem alkyl group; X ¹ and X ² are independently represented by a gold steel alkyl group, and X ³ represents CR ⁷ (R ⁸ ) (R ^{9 )} And X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ); X ¹ and X ² independently represent an emblem alkyl group, X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), and X ⁴ represents CR ¹⁰ ( R ¹¹ )(R ¹² ); X ¹ and X ² independently represent a gold steel alkyl group, and X ³ together with X ⁴ and the Q ¹ to which they are attached form a ring system of formula IIIb or a 2-phosphorus-gold alkane X ¹ and X ² independently represent an alkylene group, and X ³ together with X ⁴ and the Q ¹ to which they are attached form a ring system of formula IIIb or a 2-phosphorus-gold steel alkyl group; X ¹ and X ² Together with their connected Q ² form a ring system of formula IIIa, and X ³ and X ⁴ together with their connected Q ¹ form a ring system of formula IIIb; X ¹ and X ² and their associated Q ² together forming a 2-phosphorus-gold steel alkyl group, and X ³ together with X ⁴ and the Q ¹ to which they are attached form a 2-phosphorus-gold steel alkyl group; highly preferred embodiments of the invention include the following :X ¹ represents CR ¹ (R ² )(R ³ ), X ² represents CR ⁴ (R ⁵ )(R ⁶ ), X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), and X ⁴ represents CR ^{1 0} (R ¹¹ )(R ¹² ); X ¹ represents CR ¹ (R ² )(R ³ ), X ² represents a gold steel alkyl group, X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), and X ⁴ represents Gold steel alkyl; X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents an emblem alkyl group, X ³ represents CR ⁷ (R ⁸ ) (R ⁹ ), and X ⁴ represents an emblem alkyl group; X ¹ to X ⁴ each independently represent adamantyl; X ¹ to X ⁴ each independently represents an alkyl group emblem; X ¹ and X ² and Q ² of their attached form a ring system of formula IIIa together, and X ³ and X ⁴ and their sum Q ¹ are attached form a ring system of formula IIIb together; X ¹ and X ² are attached and their sum Q ² together form a 2-phospha - adamantyl, and X ³ and X ⁴ are and their The linked Q ¹ together form a 2-phosphorus-gold steel alkyl group; preferably, in the compound of formula III, the X ¹ system is the same as X ³ and the X ² system is the same as X ⁴ . More preferably, X ¹ is the same as X ³ and X ⁵ , X ⁷ and X ⁹ (when present), and X ² is the same as X ⁴ and X ⁶ , X ⁸ and X ¹⁰ (when present). More preferably, X ¹ to X ⁴ are the same. The X ¹ to X ⁴ optimum is the same as each of X ⁶ to X ¹⁰ (when present).

Preferably, in the compound of formula III, X ¹ and X ² represent the same substituent, X ³ and X ⁴ represent the same substituent, and X ⁵ and X ⁶ (when present) represent the same substituent, X ⁷ and X ⁸ (when present) represents the same substituent, and X ⁹ and X ¹⁰ (when present) represent the same substituent.

In the compound of formula III, K ¹ preferably represents -A ₃ -Q ³ (X ⁵ )X ⁶ , hydrogen, lower alkyl, -CF ₃ , phenyl or lower alkylphenyl. More preferably, K ¹ represents -A ₃ -Q ³ (X ⁵ )X ⁶ , hydrogen, unsubstituted C ₁ -C ₆ alkyl, unsubstituted phenyl, trifluoromethyl or C ₁ -C ₆ Alkylphenyl.

In a particularly preferred embodiment, the K ¹ system in the compound of formula III represents hydrogen.

In an alternate embodiment, wherein K ¹ does not represent hydrogen, K ¹ represents -A ₃ -Q ³ (X ⁵ )X ⁶ . Preferably, the X ⁵ system is the same as X ³ or X ¹ and the X ⁶ system is the same as X ² or X ⁴ . More preferably, the X ⁵ system is the same as both X ³ and X ¹ , and the X ⁶ system is the same as both X ² and X ⁴ . Further preferably, -A ₃ -Q ³ (X ⁵ )X ⁶ is the same as -A ₁ -Q ² (X ¹ )X ² or -A ₂ -Q ¹ (X ³ )X ⁴ . The -A ₃ -Q ³ (X ⁵ )X ^{6 is} most preferably the same as -A ₁ -Q ² (X ¹ )X ² and -A ₂ -Q ¹ (X ³ )X ⁴ .

The best system of K ¹ in the compound of formula III represents hydrogen.

Preferably, in the compound of formula III, D ¹ represents -A ₄ -Q ⁴ (X ⁷ )X ⁸ , hydrogen, lower alkyl, CF ₃ , phenyl or lower alkylphenyl, and E ¹ Represents -A ₅ -Q ⁵ (X ⁹ )X ¹⁰ , hydrogen, lower alkyl, CF ₃ , phenyl or lower alkylphenyl, or D ¹ with E ¹ and the cyclopentadiene to which they are attached The carbon of the base ring together forms an optionally substituted benzene ring. More preferably, D ¹ represents -A ₄ -Q ⁴ (X ⁷ )X ⁸ , hydrogen, phenyl, C ₁ -C ₆ alkylphenyl, unsubstituted C ₁ -C ₆ alkyl, such as a Base, ethyl, propyl, butyl, pentyl and hexyl, or CF ₃ ; E ¹ represents -A ₅ -Q ⁵ (X ⁹ )X ¹⁰ , hydrogen, phenyl, C ₁ -C ₆ alkylphenyl , unsubstituted C ₁ -C ₆ alkyl, such as methyl, ethyl, propyl, butyl, pentyl and hexyl, or -CF ₃ ; or both D ¹ and E ¹ and their The carbon atoms of the cyclopentadienyl ring together form a benzene ring, which is optionally selected from one or more selected from the group consisting of phenyl, C ₁ -C ₆ alkylphenyl, unsubstituted C ₁ -C ₆ alkyl or The group of -CF ₃ is substituted.

Suitably, when D ¹ and E ¹ together with the carbon atom of the cyclopentadienyl ring to which they are attached form an optionally substituted benzene ring, the metal M or its cation is attached to the indenyl ring system.

In a particularly preferred embodiment, the D ¹ in the compound of formula III represents hydrogen.

In an alternate embodiment, wherein D ¹ does not represent hydrogen, D ¹ represents -A ₄ -Q ⁴ (X ⁷ )X ⁸ . Preferably, X ⁸ is the same as X ⁴ or X ² and X ⁷ is the same as X ¹ or X ³ . More preferably, the X ⁸ system is the same as both X ⁴ and X ² , and the X ⁷ system is the same as X ¹ and X ³ . Further preferably, -A ₄ -Q ⁴ (X ⁷ )X ⁸ is the same as -A ₁ -Q ² (X ¹ )X ² or -A ₂ -Q ¹ (X ³ )X ⁴ . The -A ₄ -Q ⁴ (X ⁷ )X ^{8 is} most preferably the same as -A ₂ -Q ¹ (X ³ )X ⁴ and -A ₃ -Q ³ (X ⁵ )X ⁶ (if present).

In a particularly preferred embodiment, the E ¹ in the compound of formula III represents hydrogen.

In an alternate embodiment, wherein E ¹ does not represent hydrogen, and E ¹ represents -A ₅ -Q ⁵ (X ⁹ )X ¹⁰ . Preferably, the X ¹⁰ system is the same as X ⁴ or X ² and the X ⁹ system is the same as X ¹ or X ³ . More preferably, the X ¹⁰ system is the same as both X ⁴ and X ² , and the X ⁹ system is the same as X ¹ and X ³ . Further preferably, -A ₅ -Q ⁵ (X ⁹ )X ¹⁰ is the same as -A ₁ -Q ² (X ¹ )X ² or -A ₂ -Q ¹ (X ³ )X ⁴ . -A ₅ -Q ⁵ (X ⁹ )X ¹⁰ best system with -A ₁ -Q ² (X ¹ )X ² and -A ₂ -Q ¹ (X ³ )X ⁴ , and -A ³ -Q ³ ( X ⁵ )X ⁶ and -A ₄ -Q ⁴ (X ⁷ )X ⁸ (if present) are the same.

In the compound of formula III, when D ¹ and E ¹ together with the carbon atom of the cyclopentadienyl ring to which they are attached do not form a optionally substituted benzene ring, each of K ¹ , D ¹ and E ¹ is more The best lines represent the same substituents.

In an alternate preferred embodiment, D ¹ together with E ¹ and the carbon of the cyclopentadienyl ring to which they are attached form an unsubstituted benzene ring.

Highly preferred embodiments of the compound of formula III include the following, wherein: K ¹ , D ¹ and E ¹ are the same substituents as defined herein, in particular wherein K ¹ , D ¹ and E ¹ represent hydrogen; K ¹ represents hydrogen. And D ¹ together with E ¹ and the carbon of the cyclopentadienyl ring to which they are attached form an unsubstituted benzene ring; K ¹ represents -A ₃ -Q ³ (X ⁵ )X ⁶ as defined herein, And both D ¹ and E ¹ represent H; K ¹ represents -A ₃ -Q ³ (X ⁵ )X ⁶ as defined herein, and D ¹ and E ¹ and the cyclopentadienyl ring to which they are attached The carbon atoms together form an unsubstituted benzene ring; K ¹ represents -A ₃ -Q ³ (X ⁵ )X ⁶ , D ¹ represents -A ₄ -Q ⁴ (X ⁷ )X ⁸ , and E ¹ represents -A ₅ -Q ⁵ (X ⁹ )X ¹⁰ .

Particularly preferred compounds of formula III include the following, wherein both D ¹ and E ¹ represent hydrogen, or D ¹ together with E ¹ and the carbon atom of the cyclopentadienyl ring to which they are attached form an unsubstituted benzene ring In particular, a compound in which both D ¹ and E ¹ represent hydrogen.

In the compound of formula III, A ₁ and A ₂ and A ₃ , A ₄ and A ₅ (when present) preferably each independently represent a C ₁ to C ₆ alkyl group, which is optionally substituted as defined herein. , for example, by a lower alkyl group. Suitably, A ₁ and A ₂ and A ₃ , A ₄ and A ₅ (when present) may comprise a palmitic carbon atom. The lower alkylene group which A ₁ to A ₅ may represent is preferably unsubstituted. The particularly preferred lower alkylene group independently represented by A ₁ to A ₅ is -CH ₂ - or -C ₂ H ₄ -. Each of A ₁ and A ₂ and A ₃ , A ₄ and A ₅ (when present) preferably represents the same lower carbene alkyl group as defined herein, especially -CH ₂ -.

In the compound of formula III, each of Q ¹ and Q ² and Q ³ , Q ⁴ and Q ⁵ (when present) are preferably identical. Each of Q ¹ and Q ² and Q ³ , Q ⁴ and Q ⁵ (when present) preferably represents phosphorus.

It will be apparent to those skilled in the art that the compound of formula III can be used as a ligand which will coordinate with the Group VIB or Group VIIIB metal or compound thereof in the formation of the catalyst system of the present invention. Typically, the Group VIB or Group VIIIB metal or compound thereof is coordinated to one or more phosphorus, arsenic and/or antimony atoms of the compound of Formula III. It should be understood that the compound of formula III can be broadly referred to as "metal alkadiene".

Suitably, when n = 1, and L ₁ represents optionally substituted cyclopentadienyl or indenyl, the compound of formula III may contain either two cyclopentadienyl rings, two fluorenyl rings or one Indenyl and a cyclopentadienyl ring (each of which may optionally be substituted, as described herein). Such a compound may be referred to as a "sandwich compound" because the metal M or its metal cation is sandwiched between two ring systems. The individual cyclopentadienyl and/or indenyl ring systems may be substantially coplanar with respect to each other, or they may be inclined relative to each other (often referred to as a curved metal alkadiene).

Alternatively, when n = 1, and L ₁ represents an aryl group, the compounds of the invention may contain either a cyclopentadienyl group or an indenyl ring (each of which may optionally be substituted, as described herein) And an aryl ring, which is substituted as defined herein. Suitably, when n = 1 and L ₁ represents an aryl group, then the metal M series of the compound of formula III as defined herein is typically in the form of a metal cation.

In a particularly preferred embodiment of the invention, in the compound of formula III, n = 1, L ₁ is as defined herein, and m = 0.

In the compound of formula III, when n = 1, L ₁ preferably represents a cyclopentadienyl, indenyl or aryl ring, each of which is optionally substituted by one or more substituents, substituents Selected from hydrogen, lower alkyl, halo, cyano, nitro, -OR ¹⁹ , -OC(O)R ²⁰ , -C(O)R ²¹ , -C(O)OR ²² , -N(R ²³ ) R ²⁴ , -C(O)N(R ²⁵ )R ²⁶ , -C(S)(R ²⁷ )R ²⁸ , -SR ²⁹ , -C(O)SR ³⁰ , -CF ₃ or dicyclopentane An olefinic group (by this term, we mean a cyclopentadienyl, indenyl or aryl ring which L ₁ may represent, which is directly bonded to a cyclopentadienyl ring of a dicyclopentadienyl iron group), Wherein R ¹⁹ to R ³⁰ are as defined herein. More preferably, if the cyclopentadienyl, indenyl or aryl ring system which L ₁ may represent is substituted, it is preferably substituted by one or more substituents selected from unsubstituted C. _1- C ₆ alkyl, halo, cyano, -OR ¹⁹ , -OC(O)R ²⁰ , -C(O)R ²¹ , -C(O)OR ²² , -N(R ²³ )R ²⁴ , Wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent hydrogen or C ₁ -C ₆ alkyl. Still more preferably, if the cyclopentadienyl, indenyl or aryl ring system which L ₁ may represent is substituted, it is preferably one or more selected from unsubstituted C ₁ -C ₆ alkyl groups. The substituent is substituted.

When n = 1, L ₁ preferably represents cyclopentadienyl, indenyl, phenyl or naphthyl, optionally substituted, as defined herein. The cyclopentadienyl, indenyl, phenyl or naphthyl group is preferably unsubstituted. More preferably, L ₁ represents a cyclopentadienyl group, a fluorenyl group or a phenyl group, and each of the rings is unsubstituted. The L ₁ optimum system represents an unsubstituted cyclopentadienyl group.

Alternatively, when n = 0, the compounds of the invention contain only one cyclopentadienyl or indenyl ring (each of which is optionally substituted, as described herein). Such a compound may be referred to as a "semi-interlayer compound." When n = 0, then m preferably represents 1 to 5 such that the metal M of the compound of formula III has 18 electron counts. In other words, when the metal M of the compound of formula III is iron, the total number of electrons contributed by the ligand L ₂ is typically five.

In a particularly preferred embodiment of the invention, in the compound of formula III, n = 0, L ₂ is as defined herein, and m = 3 or 4, especially 3.

When n is equal to zero and m is not equal to zero in the compound of formula III, L ₂ preferably represents one or more ligands, each of which is independently selected from the group consisting of lower alkyl, halo, -CO, -P. (R ⁴³ )(R ⁴⁴ )R ⁴⁵ or -N(R ⁴⁶ )(R ⁴⁷ )R ⁴⁸ . More preferably, L ₂ represents one or more ligands, each of which is independently selected from unsubstituted C ₁ to C ₄ alkyl, halo, especially chloro, -CO, -P(R ⁴³ ) (R ⁴⁴ ) R ⁴⁵ or -N(R ⁴⁶ )(R ⁴⁷ )R ⁴⁸ , wherein R ⁴³ to R ⁴⁸ are independently selected from hydrogen, unsubstituted C ₁ to C ₆ alkyl, or aryl, such as benzene base.

Suitably, the metal M or a metal cation thereof in the compound of formula III is typically bonded to the cyclopentadienyl ring, the fluorenyl ring (if present), the cyclopentadienyl moiety, the aryl ring (if present) and/or ligand L ₂ (if present). Typically, the cyclopentadienyl moiety of the cyclopentadienyl or indenyl ring exhibits a mode of binding to the metal; however, in the cyclopentadienyl or indenyl ring Other modes of association between the alkenyl moiety and the metal, such as the triple complexation, are also encompassed by the scope of the invention.

Optimally, the compound of formula III, n = 1, m = 0 , and L ₁ system is defined herein, particularly non-substituted cyclopentadienyl group.

M preferably represents a Group VIB or VIIIB metal. In other words, the total electron count for metal M is 18.

In the compound of formula III, M preferably denotes Cr, Mo, Fe, Co or Ru or a metal cation thereof. More preferably, M represents Cr, Fe, Co or Ru or a metal cation thereof. The M is preferably selected from the group VIIIB metal or a metal cation thereof. The preferred Group VIIIB metal is Fe. While the metal M as defined herein may be in a cationic form, it is preferably substantially free of residual charge due to coordination with L ₁ and/or L ₂ as defined herein.

Particularly preferred compounds of formula III include the following: wherein: (1) X ¹ represents CR ¹ (R ² ) (R ³ ), X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), and X ³ represents CR ⁷ (R ⁸ (R ⁹ ), X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), wherein each of R ¹ to R ¹² independently represents an unsubstituted C ₁ -C ₆ alkyl group or a trifluoromethyl group, particularly Each of R ¹ to R ¹² is the same, especially wherein each of R ¹ to R ¹² represents an unsubstituted C ₁ -C ₆ alkyl group, particularly a methyl group; A ₁ and A ₂ are the same, and represents -CH ₂ -; K ¹ , D ¹ and E ¹ are the same and represent hydrogen or an unsubstituted C ₁ -C ₆ alkyl group, especially hydrogen; both Q ¹ and Q ² represent phosphorus; M represents Fe; n=1, And L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m=0.

(2) X ¹ represents CR ¹ (R ² )(R ³ ), X ² represents CR ⁴ (R ⁵ )(R ⁶ ), X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ); K ¹ represents —CH ₂ —Q ³ (X ⁵ )X ⁶ , wherein X ⁵ represents CR ¹³ (R ¹⁴ )(R ¹⁵ ), and X ⁶ represents CR ¹⁶ (R ¹⁷ ) (R ¹⁸ ); each of R ¹ to R ¹⁸ independently represents an unsubstituted C ₁ -C ₆ alkyl or trifluoromethyl group, particularly wherein each of R ¹ to R ¹⁸ is the same, especially wherein each R ^{1 is} R ¹⁸ represents an unsubstituted C ₁ -C ₆ alkyl group, particularly a methyl group; A ₁ and A ₂ are the same and represent -CH ₂ -; Q ¹ , Q ² and Q ³ each represent phosphorus; D ¹ and E ¹ is the same and represents hydrogen or unsubstituted C ₁ -C ₆ alkyl, in particular hydrogen; M represents Fe; n=1, and L ₁ represents a cyclopentadienyl group, in particular an unsubstituted cyclopentane Dienyl, and m=0.

(3) X ¹ represents CR ¹ (R ² )(R ³ ), X ² represents CR ⁴ (R ⁵ )(R ⁶ ), X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ); K ¹ represents —CH ₂ —Q ³ (X ⁵ )X ⁶ , wherein X ⁵ represents CR ¹³ (R ¹⁴ )(R ¹⁵ ), and X ⁶ represents CR ¹⁶ (R ¹⁷ ) (R ¹⁸ ); each of R ¹ to R ¹⁸ independently represents an unsubstituted C ₁ -C ₆ alkyl or trifluoromethyl group, particularly wherein each of R ¹ to R ¹⁸ is the same, especially wherein each R ^{1 is} R ¹⁸ represents an unsubstituted C ₁ -C ₆ alkyl group, particularly a methyl group; A ₁ and A ₂ are the same and represent -CH ₂ -; Q ¹ , Q ² and Q ³ each represent phosphorus; D ¹ and E ¹ together with the carbon atom of the cyclopentadienyl ring to which they are attached, form an unsubstituted benzene ring; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted ring Pentadienyl, and m=0.

(4) X ¹ represents CR ¹ (R ² )(R ³ ), X ² represents CR ⁴ (R ⁵ )(R ⁶ ), X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), wherein each of R ¹ to R ¹² independently represents an unsubstituted C ₁ -C ₆ alkyl group or a trifluoromethyl group, particularly wherein each of R ¹ to R ¹² is the same, especially Wherein each of R ¹ to R ¹² represents an unsubstituted C ₁ -C ₆ alkyl group, particularly a methyl group; A ₁ and A ₂ are the same and represent -CH ₂ -; both Q ¹ and Q ² represent phosphorus; K ¹ represents hydrogen or C ₁ -C ₆ alkyl, especially hydrogen; D ¹ together with E ¹ and the carbon atom of the cyclopentadienyl ring to which they are attached form an unsubstituted benzene ring; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m = 0.

(5) X ¹ represents CR ¹ (R ² )(R ³ ), X ² represents CR ⁴ (R ⁵ )(R ⁶ ), X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ); E ¹ represents —CH ₂ —Q ⁵ (X ⁹ )X ¹⁰ , wherein X ⁹ represents CR ³⁷ (R ³⁸ )(R ³⁹ ), and X ¹⁰ represents CR ⁴⁰ (R ⁴¹ ) (R ⁴² ); each of R ¹ to R ¹² and R ³⁷ to R ⁴² independently represents an unsubstituted C ₁ -C ₆ alkyl or trifluoromethyl group, particularly wherein each of R ¹ to R ¹² and R ^{37 is} R ⁴² is the same, especially wherein each of R ¹ to R ¹² and R ³⁷ to R ⁴² represents an unsubstituted C ₁ -C ₆ alkyl group, particularly a methyl group; A ₁ and A ₂ are the same and represent -CH ₂ -; Q ¹ , Q ² and Q ⁵ each represent phosphorus; D ¹ is the same as K ¹ and represents hydrogen or an unsubstituted C ₁ -C ₆ alkyl group, especially hydrogen; M represents Fe; n=1 And L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m=0.

(6) X ¹ represents CR ¹ (R ² )(R ³ ), X ² represents CR ⁴ (R ⁵ )(R ⁶ ), X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ); K ¹ represents —CH ₂ —Q ³ (X ⁵ )X ⁶ , wherein X ⁵ represents CR ¹³ (R ¹⁴ )(R ¹⁵ ), and X ⁶ represents CR ¹⁶ (R ¹⁷ ) (R ¹⁸ ); D ¹ represents -CH ₂ -Q ⁴ (X ⁷ )X ⁸ , wherein X ⁷ represents CR ³¹ (R ³² )(R ³³ ), and X ⁸ represents CR ³⁴ (R ³⁵ )(R ³⁶ ) ; E ¹ represents -CH ₂ -Q ⁵ (X ⁹ )X ¹⁰ , wherein X ⁹ represents CR ³⁷ (R ³⁸ )(R ³⁹ ), and X ¹⁰ represents CR ⁴⁰ (R ⁴¹ )(R ⁴² ); each R ¹ To R ¹⁸ and R ³¹ to R ⁴² independently represent unsubstituted C ₁ -C ₆ alkyl or trifluoromethyl, in particular wherein each of R ¹ to R ¹⁸ and R ³¹ to R ⁴² are the same, especially Each of R ¹ to R ¹⁸ and R ³¹ to R ⁴² represents an unsubstituted C ₁ -C ₆ alkyl group, particularly a methyl group; A ₁ and A ₂ are the same and represent -CH ₂ -; Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ each represent phosphorus; M represents Fe; n=1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m=0.

(7) X ¹ , X ² , X ³ and X ⁴ are independently represented by a gold steel alkyl group, especially wherein the steel groups alkyl groups in which X ¹ to X ⁴ represent the same; A ₁ and A ₂ are the same, and represent -CH ₂ -; K ¹ , D ¹ and E ¹ are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, especially hydrogen; both Q ¹ and Q ² represent phosphorus; M represents Fe; =1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m=0.

(8) X ¹ , X ² , X ³ and X ⁴ independently represent a gold steel alkyl group, especially wherein the steel groups alkyl groups in which X ¹ to X ⁴ represent the same; K ¹ represents -CH ₂ -Q ³ (X ⁵ X ⁶ , wherein X ⁵ and X ⁶ are independently represented by a gold steel alkyl group, especially wherein the steel groups of X ¹ to X ⁶ represent the same gold; A ₁ and A ₂ are the same, and represent -CH ₂ -; Q ¹ , Q ² and Q ³ each represent phosphorus; D ¹ and E ¹ are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, especially hydrogen; M represents Fe; n=1, and L ₁ Represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m=0.

(9) X ¹ , X ² , X ³ and X ⁴ independently represent a gold steel alkyl group, especially wherein X ¹ to X ⁴ represent the same gold steel alkyl group; K ¹ represents -CH ₂ -Q ³ (X ⁵ X ⁶ , wherein X ⁵ and X ⁶ are independently represented by a gold steel alkyl group, especially wherein the steel groups of X ¹ to X ⁶ represent the same gold; A ₁ and A ₂ are the same, and represent -CH ₂ -; Q ¹ , Q ² and Q ³ each represent phosphorus; D ¹ together with E ¹ and the carbon atom of the cyclopentadienyl ring to which they are attached form an unsubstituted benzene ring; M represents Fe; n=1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m=0.

(10) X ¹ , X ² , X ³ and X ⁴ independently represent a gold steel alkyl group, especially wherein the steel groups alkyl groups in which X ¹ to X ⁴ represent the same; A ₁ and A ₂ are the same, and represent -CH ₂ -; both Q ¹ and Q ² represent phosphorus; K ¹ represents hydrogen or unsubstituted C ₁ -C ₆ alkyl, especially hydrogen; D ¹ and E ¹ and the cyclopentadiene to which they are attached The carbon atoms of the base ring together form an unsubstituted benzene ring; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m = 0.

(11) X ¹ , X ² , X ³ and X ⁴ are independently represented by a gold steel alkyl group; K ¹ represents -CH ₂ -Q ³ (X ⁵ )X ⁶ , wherein X ⁵ and X ⁶ are independently represented by a gold alkyl alkane D ¹ represents -CH ₂ -Q ⁴ (X ⁷ )X ⁸ , wherein X ⁷ and X ⁸ independently represent a gold steel alkyl group; and E ¹ represents -CH ₂ -Q ⁵ (X ⁹ )X ¹⁰ , wherein X ⁹ and X ¹⁰ are independent of gold alkyl, especially where X ¹ to X ¹⁰ represent the same gold alkyl; A ₁ and A ₂ are the same, and represent -CH ₂ -; Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ each represent phosphorus; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m = 0.

(12) X ¹ and X ² together with the Q ² to which they are attached represent a 2-phosphorus-gold steel alkyl group; X ³ together with X ⁴ and the Q ¹ to which they are attached represent a 2-phosphorus-gold steel alkyl group ; A ₁ is the same as A ₂ and represents -CH ₂ -; K ¹ , D ¹ and E ¹ are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, especially hydrogen; Q ¹ and Both of Q ² represent phosphorus; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m = 0.

(13) X ¹ and X ² together with the Q ² to which they are attached represent a 2-phosphorus-gold steel alkyl group; X ³ together with X ⁴ and the Q ¹ to which they are attached represent a 2-phosphorus-gold steel alkyl group ; K ¹ represents -CH ₂ -Q ³ (X ⁵ )X ⁶ , wherein X ⁵ and X ⁶ together with the Q ³ to which they are attached represent a 2-phosphorus-gold steel alkyl group; A ₁ and A ₂ are the same, And represents -CH ₂ -; Q ¹ , Q ² and Q ³ each represent phosphorus; D ¹ and E ¹ are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, especially hydrogen; M represents Fe n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m = 0.

(14) X ¹ and X ² together with the Q ² to which they are attached represent a 2-phosphorus-gold steel alkyl group; X ³ together with X ⁴ and the Q ¹ to which they are attached represent a 2-phosphorus-gold steel alkyl group ; K ¹ represents -CH ₂ -Q ³ (X ⁵ )X ⁶ , wherein X ⁵ and X ⁶ together with the Q ³ to which they are attached represent a 2-phosphorus-gold steel alkyl group; A ₁ and A ₂ are the same, And represents -CH ₂ -; Q ¹ , Q ² and Q ³ each represent phosphorus; D ¹ together with E ¹ and the carbon atom of the cyclopentadienyl ring to which they are attached form an unsubstituted benzene ring; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m = 0.

(15) X ¹ and X ² together with the Q ² to which they are attached represent a 2-phosphorus-gold steel alkyl group; X ³ together with X ⁴ and the Q ¹ to which they are attached represent a 2-phosphorus-gold steel alkyl group ; A ₁ is the same as A ₂ and represents -CH ₂ -; both Q ¹ and Q ² represent phosphorus; K ¹ represents hydrogen or unsubstituted C ₁ -C ₆ alkyl, especially hydrogen; D ¹ Together with E ¹ and the carbon atom of the cyclopentadienyl ring to which they are attached, an unsubstituted benzene ring is formed; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly unsubstituted Cyclopentadienyl, and m=0.

(16) X ¹ and X ² together with the Q ² to which they are attached represent a 2-phosphorus-gold steel alkyl group; X ³ together with X ⁴ and the Q ¹ to which they are attached represent a 2-phosphorus-gold steel alkyl group ; K ¹ represents -CH ₂ -Q ³ (X ⁵ )X ⁶ , wherein X ⁵ together with X ⁶ and the Q ³ to which they are attached represent a 2-phosphorus-gold steel alkyl group; D ¹ represents -CH ₂ -Q ⁴ (X ⁷ )X ⁸ , wherein X ⁷ and X ⁸ together with the Q ⁴ to which they are attached represent a 2-phosphorus-gold steel alkyl group; and E ¹ represents —CH ₂ —Q ⁵ (X ⁹ )X ¹⁰ , wherein X ⁹ together with X ¹⁰ and the Q ⁵ to which they are attached represent a 2-phosphorus-gold steel alkyl group; A ₁ and A ₂ are the same and represent -CH ₂ -; Q ¹ , Q ² , Q ³ , Q ⁴ And Q ⁵ each represents phosphorus; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m = 0.

(17) X ¹ and X ² together with the Q ² to which they are attached form a ring system of formula IIIa, X ³ and X ⁴ together with the Q ¹ to which they are attached form a ring system of formula IIIb, wherein Y ¹ and Y ² both represent oxygen, R ⁵⁰ to R ⁵³ are independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ represent hydrogen; A ₁ and A ₂ are the same and represent -CH ₂ -; K ¹ , D ¹ and E ¹ are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, especially hydrogen; both Q ¹ and Q ² represent phosphorus; M represents Fe n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group (referred to as puc), and m = 0.

(18) X ¹ and X ² together with the Q ² to which they are attached form a ring system of formula IIIa, X ³ and X ⁴ together with the Q ¹ to which they are attached form a ring system of formula IIIb, wherein Y ¹ and Y ² both represent oxygen, R ⁵⁰ to R ⁵³ are independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ represent hydrogen; K ¹ represents -CH ₂ -Q ³ ( X ⁵ )X ⁶ , wherein X ⁵ and X ⁶ together with the Q ³ to which they are attached form a ring system of formula IIIc, wherein Y ³ represents oxygen and R ⁵⁰ to R ⁵³ are independently selected from hydrogen, unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ represent hydrogen; A ₁ and A ₂ are the same and represent -CH ₂ -; Q ¹ , Q ² and Q ³ each represent phosphorus; D ¹ and E ¹ is the same and represents hydrogen or C ₁ -C ₆ alkyl, in particular hydrogen; M represents Fe; n=1, and L ₁ represents a cyclopentadienyl group, in particular an unsubstituted cyclopentadienyl group, And m=0.

(19) X ¹ and X ² together with the Q ² to which they are attached form a ring system of formula IIIa, X ³ and X ⁴ together with the Q ¹ to which they are attached form a ring system of formula IIIb, wherein Y ¹ and Y ² both represent oxygen, R ⁵⁰ to R ⁵³ are independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ³ , and R ⁴⁹ and R ⁵⁴ represent hydrogen; K ¹ represents -CH ₂ -Q ³ ( X ⁵ )X ⁶ , wherein X ⁵ and X ⁶ together with the Q ³ to which they are attached form a ring system of formula IIIc, wherein Y ³ represents oxygen and R ⁵⁰ to R ⁵³ are independently selected from unsubstituted C ₁ - C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ represent hydrogen; A ₁ and A ₂ are the same and represent -CH ₂ -; Q ¹ , Q ² and Q ³ each represent phosphorus; D ¹ and E ¹ and The carbon atoms of the cyclopentadienyl ring to which they are attached together form an unsubstituted benzene ring; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentane Alkenyl, and m=0.

(20) X ¹ and X ² together with the Q ² to which they are attached form a ring system of formula IIIa, X ³ and X ⁴ together with the Q ¹ to which they are attached form a ring system of formula IIIb, wherein Y ¹ and Y ² both represent oxygen, R ⁵⁰ to R ⁵³ are independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ represent hydrogen; A ₁ and A ₂ are the same and represent -CH ₂ -; both Q ¹ and Q ² represent phosphorus; K ¹ represents hydrogen or unsubstituted C ₁ -C ₆ alkyl, especially hydrogen; D ¹ and E ¹ and the cyclopentene to which they are attached The carbon atoms of the dienyl ring together form an unsubstituted benzene ring; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m=0 .

(21) X ¹ and X ² together with the Q ² to which they are attached form a ring system of formula IIIa, X ³ and X ⁴ together with the Q ¹ to which they are attached form a ring system of formula IIIb, wherein Y ¹ and Y ² both represent oxygen, R ⁵⁰ to R ⁵³ are independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ represent hydrogen; K ¹ represents -CH ₂ -Q ³ ( X ⁵ )X ⁶ , wherein X ⁵ and X ⁶ together with the Q ³ to which they are attached form a ring system of formula IIIc, wherein Y ³ represents oxygen and R ⁵⁰ to R ⁵³ are independently selected from unsubstituted C ₁ - C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ represent hydrogen; D ¹ represents -CH ₂ -Q ⁴ (X ⁷ )X ⁸ , wherein X ⁷ forms a formula together with X ⁸ and the Q ⁴ to which they are attached a ring system of IIIc, wherein Y ³ represents oxygen, R ⁵⁰ to R ⁵³ are independently selected from unsubstituted C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ represent hydrogen; and E ¹ represents -CH ₂ -Q ⁵ (X ⁹ )X ¹⁰ , wherein X ⁹ together with X ¹⁰ and the Q ⁵ to which they are attached form a ring system of formula IIIe wherein Y ⁵ represents oxygen and R ⁵⁰ to R ⁵³ are independently selected from the group consisting of Substituting C ₁ -C ₆ alkyl or CF ₃ , and R ⁴⁹ and R ⁵⁴ represent hydrogen; A ₁ and A ₂ are the same, and represent -CH ₂ -; Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ each represent phosphorus; M represents Fe; n=1, and L ₁ represents a cyclopentadienyl group; particularly an unsubstituted cyclopentadienyl group, and m=0.

(22) X ¹ , X ² , X ³ and X ⁴ independently represent an emblem alkyl group, especially wherein X ¹ to X ⁴ represent the same emblem alkyl group; A ₁ and A ₂ are the same, and represent -CH ₂ - ; K ¹ , D ¹ and E ¹ are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, especially hydrogen; both Q ¹ and Q ² represent phosphorus; M represents Fe; n=1 And L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m=0.

(23) X ¹ , X ² , X ³ and X ⁴ independently represent an emblem alkyl group, especially wherein X ¹ to X ⁴ represent the same emblem alkyl group; K ¹ represents -CH ₂ -Q ³ (X ⁵ )X ⁶ , wherein X ⁵ and X ⁶ are independently represented by an emblem alkyl group, especially wherein X ¹ to X ⁶ represent the same emblem alkyl; A ₁ and A ₂ are the same, and represents -CH ₂ -; Q ¹ , Q ² And Q ³ each represents phosphorus; D ¹ and E ¹ are the same, and represent hydrogen or an unsubstituted C ₁ -C ₆ alkyl group, particularly hydrogen; M represents Fe; n=1, and L ₁ represents cyclopentane Alkenyl, especially unsubstituted cyclopentadienyl, and m=0.

(24) X ¹ , X ² , X ³ and X ⁴ independently represent an emblem alkyl group, especially wherein X ¹ to X ⁴ represent the same emblem alkyl group; K ¹ represents -CH ₂ -Q ³ (X ⁵ )X ⁶ , wherein X ⁵ and X ⁶ are independently represented by an emblem alkyl group, especially wherein X ¹ to X ⁶ represent the same emblem alkyl; A ₁ and A ₂ are the same, and represents -CH ₂ -; Q ¹ , Q ² And Q ³ each represents phosphorus; D ¹ together with E ¹ and the carbon atom of the cyclopentadienyl ring to which they are attached form an unsubstituted benzene ring; M represents Fe; n=1, and L ₁ represents cyclopentane Dienyl, especially unsubstituted cyclopentadienyl, and m=0.

(25) X ¹ , X ² , X ³ and X ⁴ independently represent an emblem alkyl group, especially wherein X ¹ to X ⁴ represent the same emblem alkyl; A ₁ and A ₂ are the same, and represent -CH ₂ - ; both Q ¹ and Q ² represent phosphorus; K ¹ represents hydrogen or unsubstituted C ₁ -C ₆ alkyl, especially hydrogen; D ¹ and E ¹ and the cyclopentadienyl ring to which they are attached The carbon atoms together form an unsubstituted benzene ring; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m = 0.

(26) X ¹ , X ² , X ³ and X ⁴ independently represent an alkylene group; K ¹ represents —CH ₂ —Q ³ (X ⁵ )X ⁶ , wherein X ⁵ and X ⁶ independently represent an emblem alkyl group; D ¹ represents -CH ₂ -Q ⁴ (X ⁷ )X ⁸ , wherein X ⁷ and X ⁸ independently represent an emblem alkyl; E ¹ represents -CH ₂ -Q ⁵ (X ⁹ )X ¹⁰ , wherein X ⁹ and X ^{The 10} series independently represents the emblem alkyl group, especially wherein X ¹ to X ¹⁰ represent the same emblem alkyl group; A ₁ and A ₂ are the same, and represent -CH ₂ -; Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ each represents phosphorus; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m = 0.

(27) X ¹ and X ³ independently represent a gold steel alkyl group, especially a gold steel alkyl group in which X ¹ and X ³ represent the same; X ² represents CR ⁴ (R ⁵ )(R ⁶ ), and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), wherein each R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ and R ¹² independently represents a C ₁ -C ₆ alkyl group or a trifluoromethyl group, particularly each of them R ⁴ to R ⁶ are the same as R ¹⁰ to R ¹² , especially wherein each of R ⁴ to R ⁶ and R ¹⁰ to R ¹² represents an unsubstituted C ₁ -C ₆ alkyl group, particularly a methyl group; A ₁ and A ₂ is the same and represents -CH ₂ -; K ¹ , D ¹ and E ¹ are the same and represent hydrogen or unsubstituted C ₁ -C ₆ alkyl, especially hydrogen; both Q ¹ and Q ² All represent phosphorus; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentadienyl group, and m = 0.

(28) X ¹ and X ³ independently represent a gold steel alkyl group, especially a gold steel alkyl group in which X ¹ and X ³ represent the same; K ¹ represents -CH ₂ -Q ³ (X ⁵ )X ⁶ , wherein X ⁵ represents a gold steel alkyl group, especially wherein X ¹ , X ³ and X ⁵ represent the same gold steel alkyl group; X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), and X ⁴ represents CR ¹⁰ (R ¹¹ ) ( R ¹² ), X ⁶ represents CR ¹⁶ (R ¹⁷ )(R ¹⁸ ), wherein each of R ⁴ to R ⁶ , R ¹⁰ to R ¹² and R ¹⁶ to R ¹⁸ independently represents an unsubstituted C ₁ -C ₆ alkane Or a trifluoromethyl group, particularly wherein each of R ⁴ to R ⁶ , R ¹⁰ to R ¹² and R ¹⁶ to R ¹⁸ are the same, especially wherein each of R ⁴ to R ⁶ , R ¹⁰ to R ¹² and R ^{16 are} R ¹⁸ represents an unsubstituted C ₁ -C ₆ alkyl group, particularly a methyl group; A ₁ and A ₂ are the same and represent -CH ₂ -; Q ¹ , Q ² and Q ³ each represent phosphorus; D ¹ and E ¹ is the same and represents hydrogen or unsubstituted C ₁ -C ₆ alkyl, especially hydrogen; M represents Fe; n=1, and L ₁ represents a cyclopentadienyl group, especially an unsubstituted ring. Pentadienyl, and m=0.

(29) X ¹ and X ³ independently represent a gold steel alkyl group, especially a gold steel alkyl group in which X ¹ and X ³ represent the same; K ¹ represents -CH ₂ -Q ³ (X ⁵ )X ⁶ , wherein X ⁵ represents a gold steel alkyl group, especially wherein X ¹ , X ³ and X ⁵ represent the same gold steel alkyl group; X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), and X ⁴ represents CR ¹⁰ (R ¹¹ ) ( R ¹² ), X ⁶ represents CR ¹⁶ (R ¹⁷ )(R ¹⁸ ), wherein each of R ⁴ to R ⁶ , R ¹⁰ to R ¹² and R ¹⁶ to R ¹⁸ independently represents an unsubstituted C ₁ -C ₆ alkane Or a trifluoromethyl group, particularly wherein each of R ⁴ to R ⁶ , R ¹⁰ to R ¹² and R ¹⁶ to R ¹⁸ are the same, especially wherein each of R ⁴ to R ⁶ , R ¹⁰ to R ¹² and R ^{16 are} R ¹⁸ represents an unsubstituted C ₁ -C ₆ alkyl group, particularly a methyl group; A ₁ and A ₂ are the same and represent -CH ₂ -; Q ¹ , Q ² and Q ³ each represent phosphorus; D ¹ and E ¹ together with the carbon atom of the cyclopentadienyl ring to which they are attached form an unsubstituted benzene ring; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly unsubstituted Cyclopentadienyl, and m=0.

(30) X ¹ and X ³ independently represent a gold steel alkyl group, especially a gold steel alkyl group in which X ¹ and X ³ represent the same; X ² represents CR ⁴ (R ⁵ ) (R ⁶ ), and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), wherein each R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ and R ¹² independently represents a C ₁ -C ₆ alkyl group or a trifluoromethyl group, particularly each of them R ⁴ to R ⁶ are the same as R ¹⁰ to R ¹² , especially wherein each of R ⁴ to R ⁶ and R ¹⁰ to R ¹² represents an unsubstituted C ₁ -C ₆ alkyl group, particularly a methyl group; A ₁ and A ₂ is the same and represents -CH ₂ -; both Q ¹ and Q ² represent phosphorus; K ¹ represents hydrogen or unsubstituted C ₁ -C ₆ alkyl, especially hydrogen; D ¹ and E ¹ and The carbon atoms of the cyclopentadienyl ring to which they are attached together form an unsubstituted benzene ring; M represents Fe; n = 1, and L ₁ represents a cyclopentadienyl group, particularly an unsubstituted cyclopentane Alkenyl, and m=0.

Specific, but non-limiting examples of bidentate ligands in this specific embodiment (II) include the following: 1,2-bis-(dimethylaminomethyl)dicyclopentadienyl iron, 1 , 2-bis-(di-tert-butylphosphinomethyl)dicyclopentadienyl iron, 1-hydroxymethyl-2-dimethylaminomethyldicyclopentadienyl iron, 1,2-double -(di-tert-butylphosphinomethyl)dicyclopentadienyl iron, 1-hydroxymethyl-2,3-bis-(dimethylaminomethyl)dicyclopentadienyl iron, 1,2 , 3-para-(di-tert-butylphosphinomethyl)dicyclopentadienyl iron, 1,2-bis-(dicyclohexylphosphinomethyl)dicyclopentadienyl iron, 1,2- Iron bis-(di-isobutylphosphinomethyl)dicyclopentadiene, iron 1,2-bis-(dicyclopentylphosphinomethyl)dicyclopentadiene, 1,2-bis-( Diethylphosphinomethyl)dicyclopentadienyl iron, 1,2-bis(di-isopropylphosphinomethyl)dicyclopentadienyl iron, 1,2-bis-(dimethylphosphino group Methyl)dicyclopentadienyl iron, 1,2-bis-(di-(1,3,5,7-tetramethyl-6,9,10-trioxo-2-phosphorus-gold steel alkyl Base)) iron dicyclopentadiene, 1,2-bis-(dimethylaminomethyl) dicyclopentadiene iron-diiodide Methane, 1,2-bis(dihydroxymethylphosphinomethyl)dicyclopentadienyl iron, 1,2-bis(diphosphinomethyl)dicyclopentadienyl iron, 1,2-bis-α , α-(P-(2,2,6,6,-tetramethylphosphin-4-one)) dimethyldicyclopentadienyl iron and 1,2-bis-(di-1,3, 5,7-Tetramethyl-6,9,10-trioxo-2-phosphorus-gold steel alkylmethyl))benzene. Nonetheless, it will be apparent to those skilled in the art that other bidentate ligands are contemplated without departing from the scope of the invention.

As mentioned herein, in yet another specific embodiment of the invention, the ligand L is a bidentate ligand (III) X ¹ (X ² )-Q ² -A of the formula (III) -R-B-Q ¹ -X ³ (X ⁴ ) wherein: A and B are as defined below for formula (IV); R represents optionally substituted cycloalkyl moiety, Q ¹ and Q ^{The 2} atomic system is bonded to the group on adjacent cyclic carbon atoms which may be employed; the groups X ¹ , X ² , X ³ and X ⁴ are as defined below for formula (IV); Q ¹ and Q ² Both are as defined below for formula (IV).

In the above formula (III), unless otherwise specified, the groups X ¹ , X ² , X ³ and X ⁴ ; A and B; and Q ¹ or Q ² are as defined herein with respect to formula (IV).

The cycloalkyl moiety preferably has from 3 up to 20 ring atoms, more preferably from 4 up to 18 ring atoms, most preferably from 4 up to 12 ring atoms, and especially from 5 to 8 ring atoms. And can be single or multi-ring. A ring atom can be a carbon or a hetero atom, and reference herein to a hetero atom refers to sulfur, oxygen, and/or nitrogen. Typically, the cycloalkyl moiety has from 2 up to 20 ring carbon atoms, more preferably from 3 up to 18 ring carbon atoms, most preferably from 3 up to 12 ring carbon atoms, and especially from 3 to 8 The ring carbon atoms may be monocyclic or polycyclic and may or may not be inserted by one or more heteroatoms. Typically, when the cycloalkyl moiety is polycyclic, it is preferably bicyclic or tricyclic. Insofar as the adjacent ring carbon atoms are saturated, the cycloalkyl moiety as defined herein may comprise an unsaturated bond and the reference to the unsaturated cycloalkyl moiety may be made accordingly. By ring atomic system is meant an atom that forms part of a cyclic backbone.

a cycloalkyl moiety, which may be unsubstituted or substituted by one or more other substituents, in addition to being interrupted by a hetero atom, the substituent being selected from an aryl group, a lower alkyl group (the alkyl group itself is visible Substituted or capped, as defined below), heteroatoms (preferably oxygen), Het, halo, cyano, nitro, -OR ¹⁹ , -OC(O)R ²⁰ , -C(O)R ²¹ , -C(O)OR ²² , -N(R ²³ )R ²⁴ , -C(O)N(R ²⁵ )R ²⁶ , -SR ²⁹ , -C(O)SR ³⁰ , -C(S)N (R ²⁷ )R ²⁸ or -CF ₃ , wherein R ¹⁹ -R ²⁸ are as defined herein below with respect to formula (IV).

The cycloalkyl moiety may be selected from the group consisting of cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, cycloheptyl, cyclooctyl, cyclodecyl, tricyclodecyl, hexahydropyridyl, morpholin Base Base, different Base Alkenyl Alkenyl, bicyclo[2,2,2]octyl, tetrahydrofuranyl, dioxononyl, O-2,3-isopropylidene-2,3-dihydroxy-ethyl, cyclopentanone, Cyclohexanone, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cyclobutenyl, cyclopentenone, cyclohexenone, gold alkyl, furan, piper, 1, 3 dioxane, 1,4 dioxane, oxocene, 7-oxodicyclo[2.2.1]heptane, pentamethylene sulfide, 1,3 dithiocarbazone, 1, 4 disulfide, furanone, lactone, butyrolactone, piperone, succinic anhydride, cis and trans 1,2-cyclohexane dicarboxylic anhydride, glutaric anhydride, tetrahydropyrrole, hexahydropyridyl , imidazole, 1,4,7 triazacyclononane, 1,5,9 triazacyclononane, thiomorpholine, thiazopyridine, 4,5-diphenyl-cyclohexyl, 4 or 5-benzene -cyclohexyl, 4,5-dimethyl-cyclohexyl, 4 or 5-methylcyclohexyl, 1,2-decahydronaphthyl, 2,3,3a,4,5,6,7,7a- Octahydro-1H-indole-5,6-yl, 3a,4,5,6,7,7a-hexahydro-1H-indole-5,6-yl, 1,2 or 3 methyl-3a,4, 5,6,7,7a-hexahydro-1H-indole-5,6-yl, trimethylene Alkyl, 3a,4,7,7a-tetrahydro-1H-indole-5,6-yl, 1,2 or 3-dimethyl-3a,4,5,6,7,7a-hexahydro-1H -茚-5,6-yl, 1,3-bis(trimethyldecyl)-3a,4,5,6,7,7a-hexahydro-3H-isobenzofuran.

Particularly preferred combinations in this particular set of embodiments include the following, wherein: -(1)X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), X ¹ Represents CR ¹ (R ² )(R ³ ), and X2 represents CR ⁴ (R ⁵ )(R ⁶ ); A and B are the same, and represent —CH ₂ —; both Q ¹ and Q ² represent phosphorus; R represents a cis-cyclohexyl group.

(2) X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), X ¹ represents CR ¹ (R ² )(R ³ ), and X ² represents CR ⁴ (R ⁵ )(R ⁶ ); A and B are the same and represent -CH ₂ -; both Q ¹ and Q ² represent phosphorus; and R represents cis-cyclopentyl.

⁽³⁾ X 3 X ⁴ are attached to the Q ¹ and their together form a 2-phospha - adamantyl, and form a 2 X ^{1 2} X ² and P together with their attached the Q - alkoxy magic A; A and B are the same and represent -CH ₂ -; both Q ¹ and Q ² represent phosphorus; and R represents cis-cyclohexyl.

(4) X ¹ , X ² , X ³ and X ⁴ represent a gold steel alkyl group; A and B are the same and represent -CH ₂ -; both Q ¹ and Q ² represent phosphorus; R represents a cis-ring Heji.

Still further preferred compounds of formula (III) include the following, wherein: R ¹ to R ¹² are alkyl and the same, and each preferably represents a C ₁ to C ₆ alkyl group, particularly a methyl group.

Particularly preferred compounds of formula (III) include the following, wherein: each of R ¹ to R ¹² is the same and represents a methyl group; A and B are the same and represent -CH ₂ -; and R represents 4,5-dimethyl- Cis-1,2-cyclohexyl.

An example of a suitable bidentate ligand of formula III is cis-1,2-bis(di-tertiary-butylphosphinomethyl)cyclohexane; cis-1,2-bis(di- Tri-butylphosphinomethyl)cyclopentane; cis-1,2-bis(di-tertiary-butylphosphinomethyl)cyclobutane; cis-1,2-bis(2-phosphine Methyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)cyclohexane; cis-1,2-bis(2-phosphinomethyl- 1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)cyclopentane; cis-1,2-bis(2-phosphinomethyl-1,3, 5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)cyclobutane; cis-1,2-bis(di-gold steel alkylphosphinomethyl)cyclohexane; Cis-1,2-bis(di-gold steel alkylphosphinomethyl)cyclopentane; cis-1,2-bis(di-gold steel alkylphosphinomethyl)cyclobutane; cis -1-(P,P-gold steel alkyl-tert-butyl-phosphinomethyl)-2-(di-t-butylphosphinomethyl)cyclohexane; cis-1-(P , P-gold steel alkyl-tert-butyl-phosphinomethyl)-2-(di-t-butylphosphinomethyl)cyclopentane; cis-1-(P,P-gold steel alkyl Tert-butyl-phosphinomethyl)-2-(di-t-butylphosphinomethyl)cyclobutane; cis-1-(2-phosphinomethyl-1,3,5, 7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl)cyclohexane; cis-1-(2-phosphino group Methyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)cyclopentane; Formula-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphine Methyl)cyclobutane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2- (two gold steel alkylphosphinomethyl) cyclohexane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold Steel alkyl)-2-(digold steel alkylphosphinomethyl)cyclopentane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9 , 10-trioxo-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)cyclobutane; cis-1-(di-tertiary-butylphosphinomethyl)-2- (two gold steel alkylphosphinomethyl) cyclohexyl Cis-1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)cyclopentane; cis-1-(di-tertiary-butyl Phosphylmethyl)-2-(di-gold-steel alkylphosphinomethyl)cyclobutane; cis-1,2-bis(2-phosphino-1,3,5-trimethyl-6,9, 10-trioxocyclo-{3.3.1.1[3.7]}mercapto)cyclohexane; cis-1,2-bis(2-phosphino-1,3,5-trimethyl-6,9, 10-trioxocyclo-{3.3.1.1[3.7]}mercapto)cyclopentane; cis-1,2-bis(2-phosphino-1,3,5-trimethyl-6,9, 10-trioxo-cyclo-{3.3.1.1[3.7]}mercapto)cyclobutane; cis-1-(2-phosphor-1,3,5-trimethyl-6,9,10-three Oxytricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)cyclohexane; cis-1-(2-phosphine-1,3, 5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)cyclopentane; Formula-1-(2-phosphorus-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-third -butylphosphinomethyl)cyclobutane; cis-1-(2-phosphorus-1,3,5-trimethyl -6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl)cyclohexane; cis-1-(2- Phosphorus-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl) ring Pentane; cis-1-(2-phospho-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-( Di-gold-steel alkylphosphinomethyl)cyclobutane; cis-1,2-bis-perfluoro(2-phosphorus-1,3,5,7-tetramethyl-6,9,10-trioxane Tricyclic and {3.3.1.1[3.7]}-mercapto)cyclohexane; cis-1,2-bis-perfluoro(2-phosphorus-1,3,5,7-tetramethyl-6,9 , 10-trioxotane and {3.3.1.1[3.7]}mercapto)cyclopentane; cis-1,2-bis-perfluoro(2-phosphorus-1,3,5,7-tetramethyl -6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)cyclobutane; cis-1,2-bis-(2-phosphorus-1,3,5,7-tetra (trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)cyclohexane; cis-1,2-bis-(2-phospho-1, 3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)cyclopentane; and cis-1,2-dual -(2-Phosphorus-1,3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]} mercapto)cyclobutane, and In the case where the palmier isomer is possible, it includes all of the cis-pair palmomers described above.

positive Examples of base bridge mating bodies include:- (2-exo, 3-exo)-bicyclo[2.2.1]heptane-2,3-bis(di-t-butylphosphinomethyl) (2-introverted, 3-intro)-bicyclo[2.2.1]heptane-2,3-bis(di-t-butylphosphinomethyl)

Examples of substituted ligands include: Cis-1,2-bis(di-tertiary-butylphosphinomethyl), 4,5-dimethylcyclohexane Cis-1,2-bis(di-tertiary-butylphosphinomethyl), 1,2,4,5 tetramethylcyclohexane Cis-1,2-bis(di-tertiary-butylphosphinomethyl), 3,6-diphenylcyclohexane Cis-1,2-bis(di-tertiary-butylphosphinomethyl)cyclohexane Cis-1,2 bis(di-tertiary-butyl(phosphinomethyl)-4,5-diphenylcyclohexane Cis-5,6-bis(di-t-butylphosphinomethyl)-1,3-bis(trimethyldecyl)-3a,4,5,6,7,7a-hexahydro- 1,3H-isobenzofuran.

It should be understood by those skilled in the art that a compound of formula (I), (II), (III), (IV) or (V) can be used as a ligand which will be coordinated with a Group 8, 9 or 10 metal compound. Position to form a metal complex for use in the present invention. Typically, the Group 8, 9 or 10 metal is coordinated to one or more of the phosphorus, arsenic and/or antimony atoms of the compound of formula (I), (II), (III), (IV) or (V).

As mentioned herein, in yet another specific embodiment of the invention, the ligand L is a bidentate ligand (IV) X1(X2)-Q ² -A-R of the formula (IV) -B-Q ¹ -X3 (X4) wherein: A and B each independently represent a lower carbene alkyl group; R represents a cyclic hydrocarbon group structure having at least one non-aromatic ring in which the Q ¹ and Q ² atomic systems are at least one Rings may be attached to the ring by adjacent ring atoms, and the ring system is substituted with at least one substituent on at least one other non-adjacent ring atom of the at least one ring; wherein adjacent ring atoms may be employed Each adjacent ring atom is not substituted to adopt an adjacent ring atom via another adjacent ring atom to the at least one ring, or an atom adjacent to the other adjacent atom but outside the at least one ring Forming other 3-8 atomic ring structures; groups X1, X2, X3, and X4 independently represent a monovalent group, up to 30 atoms, having at least one tertiary carbon atom, or X1 and X2 and/or X3 and X4 Forming together a divalent group of up to 40 atoms, having at least two tertiary carbon atoms, wherein each of the monovalent or divalent groups is via The at least one or two tertiary carbon atoms are individually bonded to the appropriate atom Q ¹ or Q ² ; and Q ¹ and Q ² each independently represent phosphorus, arsenic or antimony.

The term "another non-adjacent ring atom" is intended to mean any other ring atom in the ring that is not adjacent to the Q ¹ and Q ² atoms and may employ any of the adjacent ring atoms.

Advantageously, the ring structure of the R group in the present invention prevents excessive rigidity by avoiding the ring structure or the bridging group being involved in a ring atom adjacent to the adjacent ring atom or a non-ring atom adjacent to such adjacent atom. . Surprisingly, the inventors have discovered that it is disadvantageous to introduce the rigid into the ring structure too close to the active position, and to be more flexible than to pass through the stiffness in the immediate vicinity of the ring (by appropriate The ring substitutions provided) have found beneficial effects. This can be due to the relatively flexible limit provided by the stereoscopic effect as compared to the inflexible ring stiffness. This flexible stereoscopic restriction allows the incoming metal atoms to take the most advantageous interaction position that will be rejected by the further ring stiffness that can be used with adjacent ring atoms. Therefore, it is excluded from this aspect of the invention that it is positive on a ring atom adjacent to an adjacent ring atom. A base type bridging group, or a group thereof, such as 1,8, according to a tree brain group. These structures introduce too much rigidity into the ring near the active site.

Thus, a ring atom adjacent to the adjacent ring atom may itself be substituted as long as it does not form part of another adjacent ring structure as defined herein. Suitable substituents may be otherwise selected from those defined by at least one other non-adjacent ring atom as defined herein.

For the avoidance of doubt, references to adjacent ring atoms or adjacent groups that may employ adjacent ring atoms are not intended to claim that the two may employ one of the adjacent ring atoms themselves. By way of example, the following is joined to the Q ¹ atom via position 1 on the ring and to the cyclohexyl ring of the Q ² atom via position 2 on the ring, having two other non-adjacent ring atoms in the ring position as defined On positions 4 and 5, and two adjacent ring atoms to the ring atom can be used at positions 3 and 6.

The term non-aromatic ring means that at least one ring to which the Q ¹ and Q ² atoms are individually bonded via B and A is non-aromatic, and the aromatic group should be interpreted broadly to include not only the phenyl type structure but also Other rings of aromaticity, such as those found in the cyclopentadienyl ring of the dicyclopentadienyl iron group, but in any case, the aromatic substituents on at least one ring of the non-aromatic group are not excluded. .

References to ethylenically unsaturated compounds herein shall be taken to include any one or more unsaturated C-C bonds, such as in alkenes, alkynes, conjugated and unconjugated dienes, and functional groups. Among those found in olefins and the like.

Substituents on the at least one other non-adjacent ring atom may be selected to promote greater stability rather than the rigidity of the configuration in the cyclic hydrocarbyl structure. Thus, the substituents are selected to have a suitable size to prevent or reduce the rate of change of the non-aromatic ring configuration. Such groups may be independently selected from the group consisting of lower alkyl, aryl, het, hetero, halo, cyano, nitro, -OR ¹⁹ , -OC(O)R ²⁰ , -C(O)R ²¹ , -C(O)OR ²² , -N(R ²³ )R ²⁴ , -C(O)N(R ²⁵ )R ²⁶ , -SR ²⁹ , -C(O)SR ³⁰ , -C(S)N(R ²⁷ ) R ²⁸ or -CF ₃ , more preferably a lower alkyl or hetero group, most preferably a C ₁ -C ₆ alkyl group. Where there are two or more such other non-adjacent ring atoms in the at least one ring, they may each be independently substituted, as described in detail herein. Thus, in the case where two such other non-adjacent ring atoms are substituted, the substituents may combine to form other ring structures, such as a 3-20 atom ring structure. Such other ring structures may be saturated or unsaturated, unsubstituted or substituted by one or more substituents selected from halo, cyano, nitro, OR ¹⁹ , OC(O)R ²⁰ , C ( O) R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , SR ²⁹ , C(O)SR ³⁰ , C(S)NR ²⁷ R ²⁸ , unsubstituted or via a substituted aryl, lower alkyl (which may itself be unsubstituted or substituted or blocked, as defined herein) or unsubstituted or substituted Het, wherein R ¹⁹ to R ³⁰ each independently represent hydrogen, Unsubstituted or substituted aryl or unsubstituted or substituted lower alkyl, and/or one or more (preferably less than a total of 4) oxygen, nitrogen, sulfur, ruthenium atoms or A decyl or dialkyl fluorenyl group is inserted or a mixture thereof.

Particularly preferred other non-adjacent ring atom substituents are methyl, ethyl, propyl, isopropyl, phenyl, keto, hydroxy, decyl, amine, cyano and carboxy groups. When two or more other non-adjacent ring atoms are substituted, the preferred substituents are x,y-dimethyl, x,y-diethyl, x,y-dipropyl, x,y-di -isopropyl, x,y-diphenyl, x,y-methyl/ethyl, x,y-methyl/phenyl, saturated or unsaturated cyclopentyl, saturated or unsaturated cyclohexyl, 1, 3 substituted or unsubstituted 1,3H-furanyl, unsubstituted cyclohexyl, x,y-keto/ethyl, x,y-keto/methyl, disubstituted on a single ring atom It is contemplated that it is typically x, x-lower dialkyl. More typical substituents are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or keto, most typically methyl or ethyl or ketone The group, most typically a methyl group; wherein x and y represent the atomic positions in the at least one ring.

Further substitution of the cyclic hydrocarbyl structure is preferably such that the Q ¹ and Q ² atoms are bonded to adjacent carbon atoms. The cyclic hydrocarbyl structure may be substituted on one or more of the other ring atoms of the at least one ring, but is preferably substituted on 1, 2, 3 or 4 of such ring atoms, more preferably 1, 2 Or three, preferably on one or two such ring atoms of the at least one ring. The substituted ring atom may be carbon or a hetero group, but is preferably carbon. For example, in a ring of ring atoms, wherein the Q ¹ and Q ² atomic groups are individually bonded to the ring atoms 1 and 2, the substitution is preferably at one or more positions 4 to n-1, meaning that the 6-membered ring (position) 6 is position 4 and/or 5 in n), position 4, 5 and/or 6 in the 7-member ring, and position 4 in the 5-member ring only.

When there are two or more substituents on the at least one ring, they may combine to form another ring structure, unless excluded herein. However, it is preferred that the substituent attached to the adjacent ring atom of the adjacent ring atom is not completely combined with the substituent on the other adjacent ring to form another ring structure, since such Make the active position too rigid.

The cyclic hydrocarbyl structure substituted with A and B at adjacent positions may be employed on the at least one ring, preferably with respect to the associated cyclic linkage and the A and B substituents, having a cis configuration.

The cyclic hydrocarbon-based structure preferably has 5 to up to 30 ring atoms, more preferably 4 to up to 18 ring atoms, most preferably 4 to up to 12 ring atoms, and when it is monocyclic, especially 5 to 8 ring atoms, and in any case may be monocyclic or polycyclic. A ring atom can be a carbon or a hetero group, wherein the reference to a hetero group herein refers to sulfur, oxygen, and/or nitrogen. Typically, the cyclic hydrocarbyl structure has from 2 up to 30 ring carbon atoms, more preferably from 3 up to 18 ring carbon atoms, most preferably from 3 up to 12 ring carbon atoms, and when monocyclic, especially It is 3 to 8 ring carbon atoms, and may be monocyclic or polycyclic in any case, and may or may not be inserted by one or more hetero atoms. Typically, when the cyclic hydrocarbon group structure is polycyclic, it is preferably bicyclic or tricyclic. Insofar as the Q ¹ and Q ² atoms are bonded to each other by the use of adjacent ring atoms, the cyclic hydrocarbyl structure as defined herein may include unsaturated bonds, and the reference to the unsaturated cyclic hydrocarbyl structure should be understood accordingly. . By ring atomic system is meant an atom that forms part of a cyclic backbone.

A cyclic hydrocarbyl structure, which may be saturated or unsaturated, except that it may be inserted by a heteroatom and is as defined herein.

The cyclic hydrocarbyl structure may be selected from the group consisting of 4 and/or 5 lower alkylcyclohexane-1,2-diyl, 4 lower alkylcyclopentane-1,2-diyl, 4,5 and/or 6 Lower alkylcycloheptane-1,2-diyl, 4,5,6 and/or 7 lower alkylcyclooctane-1,2-diyl, 4,5,6,7 and/or 8 lower alkylcyclodecane-1,2-diyl, 5 and/or 6 lower alkylalkylhexahydropyridin-2,3-diyl, 5 and/or 6 lower alkyl morpholinol -2,3-diyl, O-2,3-isopropylidene-2,3-dihydroxy-ethane-2,3-diyl, cyclopentan-one-3,4-diyl, cyclohexyl Keto-3,4-diyl, 6-lower alkylcyclohexanone-3,4-diyl, 1-lower alkylcyclopentene-3,4-diyl, 1 and/or 6 low carbon Alkylcyclohexene-3,4-diyl, 2 and/or 3 lower alkylcyclohexadiene-5,6-diyl, 5 lower alkylcyclohexen-4-one-1,2 -diyl, gold steel alkyl-1-2-diyl, 5 and/or 6 lower alkyl tetrahydropyran-2,3-diyl, 6-lower alkyl dihydropyran-2 3-diyl, 2-lower alkyl 1,3 dioxane-5,6-diyl, 5 and/or 6 lower alkyl-1,4-dioxolan-2,3-di Base, 2-lower alkyl penta Sulfide 4,5-diyl, 2-lower alkyl-1,3-dithiorepine-5,6-diyl, 2 and/or 3-lower alkyl 1,4-dithiorepine -5,6-diyl, tetrahydro-furan-2-one-4,5-diyl, δ-valerolactone 4,5-diyl, γ-butyrolactone 3,4-diyl, 2H- Dihydropiperone 5,6-diyl, glutaric anhydride 3,4-diyl, 1-lower alkyltetrahydropyrrole-3,4-diyl, 2,3 dilower alkyl hexahydropyridyl -5,6-diyl, 2-lower alkyldihydroimidazole-4,5-diyl, 2,3,5 and/or 6 lower alkyl-1,4,7-triazacyclononane -8,9-diyl, 2,3,4 and/or 10 lower alkyl-1,5,9-triazacyclodecane 6,7-diyl, 2,3-di lower alkyl sulfide Defosolin-5,6-diyl, 2-lower alkyl-thiazolidin-4,5-diyl, 4,5-diphenyl-cyclohexane-1,2-diyl, 4 and /or 5-phenyl-cyclohexane-1,2-diyl, 4,5-dimethyl-cyclohexane-1,2-diyl, 4 or 5-methylcyclohexane-1,2 -diyl, 2,3,4 and/or 5 lower alkyl-decahydronaphthalene-8,9-diyl, bicyclo[4.3.0]nonane-3,4-diyl, 3a,4, 5,6,7,7a-hexahydro-1H-indole-5,6-diyl, 1,2 and/or 3 methyl-3a,4,5,6,7,7a-hexahydro-1H-indole -5,6-diyl, octahydro-4,7-methylalkyl-indole-1,2-diyl, 3a,4,7,7a-tetrahydro-1H-indole-5,6-diyl, 1 , 2 and/or 3-dimethyl-3a, 4,5,6,7,7a-hexahydro-1H-indole-5,6-diyl, 1,3-bis(trimethyldecyl)- 3a, 4, 5, 6, 7, 7a-hexahydro-3H-isobenzofuran-5,6-diyl.

Some typical structures are shown below, wherein R', R", R''', R"", etc. are defined in the same manner as the substituents on the at least one other non-adjacent ring atom above, but may also be Hydrogen, or if directly bonded to a hetero atom, indicates that the hetero atom is unsubstituted and may be the same or different, and wherein at least one R' atom is not hydrogen, or if directly bonded to a hetero atom, the hetero atom is Unsubstituted. The bis-methylene chain of phosphorus (not shown) is shown in each case.

In the context of this document, all such stereoisomers are intended where more than one stereoisomeric form is possible. However, at least one substituent on at least one other non-adjacent ring atom of the at least one ring preferably extends in the trans-direction relative to the A and/or B atoms, that is, on the opposite side of the ring. Extend outwards.

Preferably, the cyclic hydrocarbyl structure is bonded to A and B to form a cis-1,2-cyclic hydrocarbyl structure, or in any case, two adjacent to each of A and B may be employed between adjacent ring atoms. The bond is in cis.

Typically, the group X ¹ represents CR ¹ (R ² )(R3), X ² represents CR ⁴ (R ⁵ )(R ⁶ ), X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), wherein R ¹ to R ¹² represent lower alkyl, aryl or het.

Particularly preferred are the organic groups R ¹ -R ³ , R ⁴ -R ⁶ , R ⁷ -R ⁹ and/or R ¹⁰ -R ¹² , or R ¹ -R ⁶ and/or R ⁷ -R ¹² , When combined with its individual tertiary carbon atoms, it forms a complex group which is at least sterically hindered as a third-butyl group. In this regard, steric hindrance is as described in CMasters "Homogeneous Transition Metal Catalysis - A Mild Technique", published by Chapman and Hall, 1981, page 14 and subsequent discussion. These stereo groups may be cyclic, partially cyclic or acyclic. When cyclic or partially cyclic, the group may be substituted or unsubstituted, or saturated or unsaturated. The cyclic or partially cyclic group preferably contains (including a tertiary carbon atom) C ₄ - C ₃₄ , more preferably C ₈ - C ₂₄ , most preferably a C ₁₀ - C ₂₀ carbon atom in the cyclic structure. . The cyclic structure may be substituted by one or more substituents selected from the group consisting of halo, cyano, nitro, OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , SR ²⁹ , C(O)SR ³⁰ , C(S)NR ²⁷ R ²⁸ , aryl or Het, wherein R ¹⁹ to R ³⁰ each independently represent hydrogen, aryl Or a lower alkyl group, and/or inserted by one or more oxygen or sulfur atoms or by a decyl or dialkyl fluorenyl group.

In particular, when it is cyclic, X ¹ , X ² , X ³ and/or X ⁴ may represent an emblem alkyl, positive Base, 1-positive Dialkyl or gold alkyl, or X ¹ and X ² together with the Q ² to which they are attached form an optionally substituted 2-Q ² -tricyclic [3.3.1.1{3,7}] fluorenyl group or a derivative thereof, or X ¹ form a ring system of formula 1a with the ² X ² and their connected the Q

Similarly, X ³ together with X ⁴ and the Q ¹ to which they are attached may form an optionally substituted 2-Q1-tricyclic [3.3.1.1{3,7}] fluorenyl group or a derivative thereof, or X ³ and X ⁴ together with their connected Q ¹ can form a ring system of formula 1b

Alternatively, one or more of the groups X ¹ , X ² , X ³ and/or X ⁴ may represent the solid phase to which the ligand is attached.

Particularly preferred is when X ¹ , X ² , X ³ and X ⁴ , or X ¹ and X ^{2 are} accompanied by their individual Q ² atoms, and X ³ and X ^{4 are} accompanied by their individual Q ¹ atoms, or X ¹ and X ³ are the same, however, X ² and X ⁴ are different but are identical to each other.

R ¹ to R ¹² each independently represent lower alkyl, aryl or Het; R ¹⁹ to R ³⁰ each independently represent hydrogen, lower alkyl, aryl or Het, and may be substituted by one or more of oxygen, sulfur and hydrazine. An atom or a decyl or dialkyl fluorenyl group or a mixture thereof; R ⁴⁹ , R ⁵⁴ and R ⁵⁵ , when present, each independently represent a hydrogen, lower alkyl or aryl group; R ⁵⁰ to R ⁵³ , when present When independently, each represents lower alkyl, aryl or Het; Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ , when present, each independently represents oxygen, sulfur or N-R ⁵⁵ , wherein R ⁵⁵ represents Hydrogen, lower alkyl or aryl.

R ¹ to R ¹² preferably each independently represent a lower alkyl group or an aryl group. More preferably, R ¹ to R ¹² independently represent a C ₁ to C ₆ alkyl group, a C ₁ -C ₆ alkylphenyl group (wherein the phenyl group is optionally substituted, as defined herein) or a phenyl group (wherein the phenyl group) The aryl group as defined herein is substituted as appropriate). More preferably, R ¹ to R ¹² each independently represent a C ₁ to C ₆ alkyl group, which is optionally substituted with an alkyl group as defined herein. R ¹ to R ¹² are each preferably an unsubstituted C ₁ to C ₆ alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or the third- Butyl, pentyl, hexyl and cyclohexyl, especially methyl.

In a particularly preferred embodiment of the invention, R ¹ , R ⁴ , R ⁷ and R ¹⁰ each represent the same lower alkyl, aryl or Het moiety, as defined herein, R ² , R ⁵ , R ⁸ and R ¹¹ each represent the same lower alkyl, aryl or Het moiety, as defined herein, and R ³ , R ⁶ , R ⁹ and R ¹² each represent the same lower alkyl, An aryl or Het moiety, as defined herein. More preferably, R ¹ , R ⁴ , R ⁷ and R ¹⁰ each represent the same C ₁ -C ₆ alkyl group, especially an unsubstituted C ₁ -C ₆ alkyl group, such as methyl, ethyl, or -propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl or cyclohexyl; R ² , R ⁵ , R ⁸ and R ¹¹ each independently represent the same as defined above C ₁ -C ₆ alkyl; and R ³ , R ⁶ , R ⁹ and R ¹² each independently represent the same C ₁ -C ₆ alkyl group as defined above. For example, R ¹ , R ⁴ , R ⁷ and R ¹⁰ each represent a methyl group; R ² , R ⁵ , R ⁸ and R ¹¹ each represent an ethyl group; and R ³ , R ⁶ , R ⁹ and R ¹² each represent a positive- Butyl or n-pentyl.

In a particularly preferred embodiment of the invention, each R ¹ to R ¹² group represents the same lower alkyl, aryl or Het moiety, as defined herein. When it is an alkyl group, each of R ¹ to R ¹² preferably represents the same C ₁ to C ₆ alkyl group, particularly an unsubstituted C ₁ -C ₆ alkyl group such as methyl, ethyl or n-propyl. Base, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl and cyclohexyl. More preferably, each of R ¹ to R ¹² represents a methyl group or a tri-butyl group, and most preferably a methyl group.

When used herein, the compounds of formula I, A and B represented by the "lower alkylidene group" includes C ₁ to C ₁₀ groups which may be bonded at two places on the group, whereby The group Q ¹ or Q ^{2 is} attached to the R group, while in other respects is defined in the same manner as the "lower alkyl group" below. Even so, the methylene system is the best.

As used herein, the term "lower alkyl" or "alkyl" means C ₁ to C ₁₀ alkyl and includes methyl, ethyl, vinyl, propyl, propenyl, butyl, Butenyl, pentyl, pentenyl, hexyl, hexenyl and heptyl. Unless otherwise indicated, alkyl groups, including lower alkyl groups, may be linear or branched when there are sufficient numbers of carbon atoms (excellent branched groups include tert-butyl and isopropyl), Saturated or unsaturated, cyclic, acyclic or partially cyclic/acyclic, unsubstituted, substituted or blocked by one or more substituents selected from halo, cyano, nitro, OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , SR ²⁹ , C(O)SR ³⁰ , C( S)NR ²⁷ R ²⁸ , unsubstituted or substituted aryl or unsubstituted or substituted Het, wherein R ¹⁹ to R ³⁰ each independently represent hydrogen, halo, unsubstituted or substituted aryl or Unsubstituted or substituted lower alkyl, or in the case of R ²¹ , halo, nitro, cyano and amine, and/or one or more (preferably less than 4) Oxygen, sulfur, helium atoms or are inserted by a decyl or dialkyl fluorenyl group or a mixture thereof.

As used herein, the term "Ar" or "aryl" includes five- to ten-members, preferably five or six to ten members of a carbon-cyclic aromatic or pseudoaromatic group, such as phenyl, ring. a pentadienyl group and a fluorenyl anion and a naphthyl group, these groups may be unsubstituted or substituted by one or more substituents selected from unsubstituted or substituted aryl, lower alkyl groups (this The group itself may be unsubstituted or substituted or blocked, as defined herein), Het (this group may itself be unsubstituted or substituted or blocked, as defined herein), halo, cyano, nitro , OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , SR ²⁹ , C(O)SR ³⁰ or C (S)NR ²⁷ R ²⁸ , wherein R ¹⁹ to R ³⁰ each independently represent hydrogen, unsubstituted or substituted aryl or lower alkyl (the alkyl group itself may be unsubstituted or substituted or blocked, As defined herein, or in the case of R ²¹ , is additionally a halo, nitro, cyano or amine group.

The term "alkenyl" as used herein, means C ₂ to C ₁₀ alkenyl, and includes ethenyl, propenyl, butenyl, pentenyl, and hexenyl. Unless otherwise indicated, an alkenyl group may be linear or branched, saturated or unsaturated, cyclic, acyclic or partially cyclic/acyclic, unsubstituted, when there are sufficient numbers of carbon atoms. Substituted or blocked with one or more substituents selected from halo, cyano, nitro, OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , SR ²⁹ , C(O)SR ³⁰ , C(S)NR ²⁷ R ²⁸ , unsubstituted or substituted aryl or unsubstituted or substituted Het, Wherein R ¹⁹ to R ³⁰ are as defined above for alkyl, and/or by one or more (preferably less than 4) oxygen, sulfur, halogen atoms or by a decyl or dialkyl fluorenyl group or Its mixture.

When used herein, "alkynyl" means a term based C ₂ to C ₁₀ alkynyl groups, and include ethynyl, propynyl, butynyl, pentynyl and hexynyl. Unless otherwise indicated, when there are sufficient carbon atoms, the alkynyl group may be linear or branched, saturated or unsaturated, cyclic, acyclic or partially cyclic/acyclic, unsubstituted, Substituted or blocked with one or more substituents selected from halo, cyano, nitro, OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , SR ²⁹ , C(O)SR ³⁰ , C(S)NR ²⁷ R ²⁸ , unsubstituted or substituted aryl or unsubstituted or substituted Het, Wherein R ¹⁹ to R ³⁰ are as defined above for alkyl, and/or by one or more (preferably less than 4) oxygen, sulfur, halogen atoms or by a decyl or dialkyl fluorenyl group or Its mixture.

The terms "subalkyl", "aralkyl", "alkylaryl", "semiarylalkyl" or the like, in the absence of the opposite information, shall be taken as "alkyl" according to the above Definition, in terms of the alkyl or alk (alkane) moiety of the group of interest.

The above Ar or aryl may be bonded by one or more covalent bonds, but the reference to "subaryl" or "heteroarylalkyl" or the like may be clarified as two covalent bonds. Linkage, and in other respects as defined by Ar or aryl above, with respect to the secondary aryl moiety of the group of interest. References to "alkaryl", "aralkyl" or the like should be taken to refer to the above Ar or aryl, as far as the Ar or aryl moiety of the group of interest is concerned.

The halogen group to which the above-mentioned group may be substituted or blocked includes a fluorine group, a chlorine group, a bromine group, and an iodine group.

As used herein, the term "Het" includes a four- to twelve-membered, preferably four- to ten-membered ring system containing one or more heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur. And mixtures thereof, and the ring contains no, one or more double bonds, or may be non-aromatic, partially aromatic or wholly aromatic in character. This ring system can be monocyclic, bicyclic or fused. Each of the "Het" groups identified herein may be unsubstituted or substituted with one or more substituents selected from the group consisting of halo, cyano, nitro, keto, and lower alkyl (the alkyl group) May be unsubstituted or substituted or capped, as defined herein, -OR ¹⁹ , -OC(O)R ²⁰ , -C(O)R ²¹ , -C(O)OR ²² , -N(R ²³ ) R ²⁴ , -C(O)N(R ²⁵ )R ²⁶ , -SR ²⁹ , -C(O)SR ³⁰ or -C(S)N(R ²⁷ )R ²⁸ , wherein each of R ¹⁹ to R ³⁰ Independently represents hydrogen, unsubstituted or substituted aryl or lower alkyl (which may itself be unsubstituted or substituted or blocked, as defined herein) or, in the case of R ²¹ , halogen Base, nitro, amine or cyano group. Thus, the term "Het" includes some groups, such as, as the case may be, a nitrogen tetradecyl group, a tetrahydropyrrolyl group, an imidazolyl group, a fluorenyl group, a furyl group, Azolyl, different Azolyl, Diazolyl, thiazolyl, thiadiazolyl, triazolyl, Triazolyl, thiatriazole, oxime Base, morpholinyl, pyrimidinyl, pyridyl Base, quinolyl, isoquinolyl, hexahydropyridyl, pyrazolyl and hexahydropyridyl base. The substitution on Het can be on the carbon atom of the Het ring or, where appropriate, on one or more heteroatoms.

The "Het" group can also be in the form of an N oxide.

The term heteroalkyl, as used herein, means nitrogen, oxygen, sulfur or mixtures thereof.

Gold steel alkyl, emblem alkyl, positive Base or 1-positive A dienyl group, optionally containing one or more substituents other than a hydrogen atom, selected from the group consisting of lower alkyl, -OR ¹⁹ , -OC(O)R ²⁰ , halo, nitro, -C(O) R ²¹ , -C(O)OR ²² , cyano, aryl, -N(R ²³ )R ²⁴ , -C(O)N(R ²⁵ )R ²⁶ , -C(S)(R ²⁷ )R ²⁸ , -SR ²⁹ , -C(O)SR ³⁰ , -CF ₃ , -P(R ⁵⁶ )R ⁵⁷ , -PO(R ⁵⁸ )(R ⁵⁹ ), -PO ₃ H ₂ , -PO(OR ⁶⁰ )( OR ⁶¹ ) or -SO ₃ R ⁶² , wherein R ¹⁹ -R ³⁰ , lower alkyl, halo, cyano and aryl are as defined herein, and R ⁵⁶ to R ⁶² each independently represent hydrogen, lower alkyl , aryl or Het.

Appropriately, when gold steel alkyl, emblem alkyl, positive Base or 1-positive When the dienyl group is substituted by one or more substituents as defined above, highly preferred substituents include unsubstituted C ₁ to C ₈ alkyl, -OR ¹⁹ , -OC(O)R ²⁰ , phenyl, -C(O)OR ²² , fluoro, -SO ₃ H, -N(R ²³ )R ²⁴ , -P(R ⁵⁶ )R ⁵⁷ , -C(O)N(R ²⁵ )R ²⁶ and -PO( R ⁵⁸ )(R ⁵⁹ ), -CF ₃ , wherein R ¹⁹ represents hydrogen, unsubstituted C ₁ -C ₈ alkyl or phenyl, R ²⁰ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ Each independently represents hydrogen or an unsubstituted C ₁ -C ₈ alkyl group, and R ⁵⁶ to R ⁵⁹ each independently represent an unsubstituted C ₁ -C ₈ alkyl group or a phenyl group. In a particularly preferred embodiment, the substituent is a C ₁ to C ₈ alkyl group, more preferably a methyl group, such as found in a 1,3 dimethyl fund steel alkyl group.

Suitably, gold steel alkyl, emblem alkyl, positive Base or 1-positive The dienyl group, in addition to the hydrogen atom, may comprise up to 10 substituents as defined above, preferably up to 5 substituents as defined above, more preferably up to 3 substituents as defined above. Appropriately, when gold steel alkyl, emblem alkyl, positive Base or 1-positive A dienyl group, which, in addition to a hydrogen atom, contains one or more substituents as defined herein, each substituent is preferably the same. Preferred substituents are unsubstituted C ₁ -C ₈ alkyl and trifluoromethyl, especially unsubstituted C ₁ -C ₈ alkyl, such as methyl. Highly preferable gold steel alkyl, emblem alkyl, positive Base or 1-positive The dienyl group contains only a hydrogen atom, meaning that the gold steel alkyl group, the emblem alkyl group, the positive Base or 1-positive The dienyl group has not been replaced.

When more than one gold steel alkyl, emblem alkyl, positive Base or 1-positive When a dienyl group is present in the compound of formula I, each such group is preferably the same.

2-Q ² (or Q ¹ )-tricyclic [3.3.1.1.{3,7}] fluorenyl (for convenience, it is hereinafter referred to as 2-inter-gold steel alkyl, of which 2-position - Gold steel alkyl is a reference to Q ¹ or Q ² as an arsenic, antimony or phosphorus atom, meaning 2-arsenic-gold steel alkyl and/or 2-indene-gold steel alkyl and/or 2-phosphorus- The gold steel alkyl group, preferably a 2-phosphorus-gold steel alkyl group, may optionally contain one or more substituents in addition to a hydrogen atom. Suitable substituents include those as defined herein with respect to the gold alkyl group. Highly preferred substituents include lower alkyl, especially unsubstituted C ₁ -C ₈ alkyl, especially methyl, trifluoromethyl, -OR ¹⁹ , wherein R ¹⁹ is as defined herein, especially Substituted C ₁ -C ₈ alkyl or aryl, and 4-dodecylphenyl. When the 2-inter-gold steel alkyl group contains more than one substituent, each substituent is preferably the same.

The 2-inter-gold steel alkyl group is preferably substituted at one or more of the 1, 3, 5 or 7 positions by a substituent as defined herein. The 2-inter-gold steel alkyl group is more preferably substituted at each of the 1, 3 and 5 positions. Suitably, such an arrangement means that the Q atomic system of the 2-meta-gold steel alkyl group is bonded to a carbon atom in the gold steel alkyl skeleton having no hydrogen atom. The 2-inter-gold steel alkyl group is substituted at each of the 1, 3, 5 and 7 positions. When the 2-inter-gold steel alkyl group contains more than one substituent, each substituent is preferably the same. Particularly preferred substituents are unsubstituted C ₁ -C ₈ alkyl and haloalkyl, especially unsubstituted C ₁ -C ₈ alkyl, such as methyl, with fluorinated C ₁ -C ₈ alkane Base, such as trifluoromethyl.

The 2-inter-gold steel alkyl group preferably represents an unsubstituted 2-m--gold steel alkyl group or a 2-m-substituent substituted with one or more unsubstituted C ₁ -C ₈ alkyl substituent groups. Gold steel alkyl, or a combination thereof.

The 2-inter-gold steel alkyl group preferably contains a hetero atom other than the 2-Q atom in the 2-inter-gold steel alkyl skeleton. Suitable other heteroatoms include oxygen and sulfur atoms, especially oxygen atoms. More preferably, the 2-inter-gold steel alkyl group contains one or more other heteroatoms at the 6, 9 and 10 positions. More preferably, the 2-inter-gold steel alkyl group contains another hetero atom at each of the 6, 9 and 10 positions. When the 2-inter-gold steel alkyl group contains two or more other hetero atoms in the 2-m-gold steel alkyl skeleton, each of the other hetero atoms is preferably the same. More preferably, the 2-inter-gold steel alkyl group, which may optionally be substituted by one or more substituents as defined herein, comprises oxygen at the 6th, 9th and 10th positions of the 2-inter-gold steel alkyl skeleton. atom.

The 2-inter-gold steel alkyl group preferably contains one or more oxygen atoms in the 2-inter-gold steel alkyl skeleton.

A highly preferred 2-inter-gold steel alkyl group as defined herein includes 2-phosphorus-1,3,5,7-tetramethyl-6,9,10-trioxy gold steel alkyl, 2-phosphorus-1 ,3,5-trimethyl-6,9,10-trioxy gold steel alkyl, 2-phosphorus-1,3,5,7-tetrakis(trifluoromethyl)-6,9,10-trioxane Gold steel alkyl and 2-phosphorus-1,3,5-tris(trifluoromethyl)-6,9,10-trioxy gold steel alkyl. The 2-phosphorus-gold steel alkyl group is preferably selected from the group consisting of 2-phosphorus-1,3,5,7-tetramethyl-6,9,10-trioxy gold steel alkyl or 2-phosphorus-1,3. 5,-Trimethyl-6,9,10-trioxy gold steel alkyl.

When more than one 2-inter-gold steel alkyl group is present in the compound of formula I, each 2-inter-gold steel alkyl group is preferably the same.

The 2-inter-gold steel alkyl group can be produced by a method known to those skilled in the art. Suitably, certain 2-phosphorus-gold steel alkyl compounds are available from Cytec Canada, Canada. Similarly, the corresponding 2-inter-gold steel alkyl compounds of Formula I and the like can be obtained from the same supplier or by a similar process.

Preferred embodiments of the invention include the following, wherein X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), and X ¹ represents CR ¹ (R ² ) (R ³ ), and X ² represents CR ⁴ (R ⁵ )(R ⁶ ); X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), and X ¹ together with X ² and the Q ² to which they are attached form a 2-phosphorus-gold steel alkyl group; X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ) And X ¹ and X ² together with the Q ² to which they are attached form a ring system of formula 1a; X ³ represents ^{CR 7 (R 8) (R} 9), X 4 represents adamantyl, and X ^{1 2} together with the phosphorus form a 2 X ² and their connections of the Q - adamantyl; X ³ represents ^{CR 7 (R 8) (R} 9), X 4 represents adamantyl, X ¹ and X ² are attached to the Q ² form and their ring system of formula 1a together; X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), X ⁴ represents a gold steel alkyl group, X ¹ represents CR ¹ (R ² )(R ³ ), and X ² represents CR ⁴ (R ⁵ )(R ⁶ ) ; X ³ represents ^{CR 7 (R 8) (R} 9), X 4 represents an alkyl group emblem, and form a 2 X ^{1 2} X ² and P together with their attached the Q - adamantyl; X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), X ⁴ represents an emblem alkyl group, X ¹ represents CR ¹ (R ² )(R ³ ), and X ² represents CR ⁴ (R ⁵ )(R ⁶ ); X ³ and The X ⁴ series independently represents a gold steel alkyl group, and X ¹ and X ² together with the Q ² to which they are attached form a 2-phosphorus-gold steel alkyl group; X ³ and X ⁴ systems independently represent a gold steel alkyl group, and X ¹ together with X ² and the Q ² to which they are attached form a ring system of formula 1a; X ³ and X ⁴ independently represent a gold steel alkyl group, X ¹ represents CR ¹ (R ² )(R ³ ), and X ² represents CR ⁴ (R ⁵ )(R ⁶ ); X ¹ , X ² , X ³ And X ⁴ represents a gold steel alkyl group; X ³ together with X ⁴ and the Q ¹ to which they are attached may form a ring system of formula 1b And X ¹ and X ² together with the Q ² to which they are attached form a ring system of formula 1a; X ³ and X ⁴ independently represent emblem alkyl-based, and phosphorus form a 2 X ^{1 2} X ^2, together with their attached and the Q - adamantyl; X ³ X ⁴ are attached to the Q ¹ and their Together, the ring system of formula 1b can be formed And X ¹ and X ² together with the Q ² to which they are attached form a 2-phosphorus-gold steel alkyl group; X ³ and X ⁴ independently represent an alkylene group, and X ¹ represents CR ¹ (R ² ) (R ^{3 )} And X ² represents CR ⁴ (R ⁵ )(R ⁶ ); X ³ together with X ⁴ and the Q ¹ to which they are attached may form a ring system of formula 1b X ¹ represents CR ¹ (R ² )(R ³ ), and X ² represents CR ⁴ (R ⁵ )(R ⁶ ); X ³ together with X ⁴ and the Q ¹ to which they are attached form a 2-phosphorus-gold steel alkyl, and X ¹ and X ² are attached and their sum Q ² together form a 2-phospha - adamantyl.

A highly preferred embodiment of the present invention includes the following, wherein: X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), and X ¹ represents CR ¹ (R ^{2 )} (R ³ ), and X ² represents CR ⁴ (R ⁵ )(R ⁶ ); especially wherein R ¹ -R ¹² are methyl.

Preferably, in the compound of formula IV, the X ³ system is the same as X ⁴ and/or the X ¹ system is the same as X ² .

Particularly preferred combinations in the present invention include the following, wherein: -(1)X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), and X ¹ represents CR ¹ (R ² )(R ³ ), and X ² represents CR ⁴ (R ⁵ )(R ⁶ ); A and B are the same and represent —CH ² —; both Q ¹ and Q ² represent phosphorus, linked R groups to positions 1 and 2 of the ring; R represents 1,2 cis-5,6-dimethylcyclohexyl.

(2) X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), X ¹ represents CR ¹ (R ² )(R ³ ), and X ² represents CR ⁴ (R ⁵ )(R ⁶ ); A and B are the same and represent -CH ₂ -; both Q ¹ and Q ² represent phosphorus, which is bonded to the R group at ring positions 1 and 2; R represents 1,2-cis-5-methylcyclopentyl.

⁽³⁾ X 3 X ⁴ are attached to the Q ¹ and their together form a 2-phospha - adamantyl, and form a 2 X ^{1 2} X ² and P together with their attached the Q - alkoxy magic A; A and B are the same and represent -CH ₂ -; both Q ¹ and Q ² represent phosphorus, linked to the R group at ring positions 1 and 2; R represents 1,2 cis -5, 6-Dimethylcyclohexyl.

(4) X ¹ , X ² , X ³ and X ⁴ represent a gold steel alkyl group; A and B are the same and represent -CH ₂ -; both Q ¹ and Q ² represent phosphorus, which is linked to the ring position 1 And the R group on 2; R represents 1,2 cis-5,6-dimethylcyclohexyl.

In the compounds of Formula I-V, A is the preferred system B each independently represent a C ₁ to C ₆ alkylidene, optionally substituted lines which, as defined herein, for example substituted lower alkyl. The lower alkylene group represented by A and B is preferably unsubstituted. The particularly preferred lower alkylene group independently represented by A and B is -CH ₂ - or -C ₂ H ₄ -. Each of A and B represents the best system the same as the lower sub-group as defined herein, particularly -CH ₂ -.

Still further preferred compounds of formula I-V include the following, wherein: R ¹ to R ¹² are alkyl and the same, and each preferably represents a C ₁ to C ₆ alkyl group, particularly a methyl group.

Particularly preferred compounds of the formula (IV) include the following, wherein: each of R ¹ to R ¹² is the same and represents a methyl group; A and B are the same and represent -CH ₂ -; and R represents 4,5-dimethyl- Cis-1,2-cyclohexyl.

An example of a suitable bidentate ligand of formula IV is cis-1,2-bis(di-tertiary-butylphosphinomethyl)-4,5-dimethylcyclohexane; cis-1 ,2-bis(di-t-butylphosphinomethyl)-5-methylcyclopentane; cis-1,2-bis(2-phosphinomethyl-1,3,5,7- Tetramethyl-6,9,10-trioxy-gold steel alkyl)-4,5-dimethylcyclohexane; cis-1,2-bis(2-phosphinomethyl-1,3, 5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-5-methylcyclopentane; cis-1,2-bis(di-gold steel alkylphosphinomethyl -4,5-dimethylcyclohexane; cis-1,2-bis(di-gold steel alkylphosphinomethyl)-5-methylcyclopentane; cis-1-(P, P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl)-4,5-dimethylcyclohexane; cis-1-( P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-tertiary-butylphosphinomethyl)-5-methylcyclopentane; cis-1-(2) -phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)4, 5-dimethyl Hexane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-third -butylphosphinomethyl)-5-methylcyclopentane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxane - gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-5-methylcyclohexane; cis-1-(2-phosphinomethyl-1,3,5,7- Tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-5-methylcyclopentane; cis-1-(2-phosphine Methyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl)cyclobutane; cis -1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-dimethylcyclohexane; cis-1-(di- Third-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-5-methylcyclopentane; cis-1,2-bis(2-phosphine-1,3, 5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4,5-dimethylcyclohexane; cis-1,2-dual ( 2-phosphorus-1,3,5-trimethyl-6,9,10- Trioxocyclo-{3.3.1.1[3.7]}mercapto)-5-methylcyclopentane; cis-1-(2-phospho-1,3,5-trimethyl-6,9, 10-trioxotricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)-4,5-dimethylcyclohexane; cis- 1-(2-Phosphorus-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]} fluorenyl)-2-(di-third-butyl) Phosphinylmethyl)-5-methylcyclopentane; cis-1-(2-phospho-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3. 1.1[3.7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-dimethylcyclohexane; cis-1-(2-phosphorus-1,3,5- Trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl)-5-methylcyclopentane; Cis-1,2-bis-perfluoro(2-phospho-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}-fluorenyl -4,5-Dimethylcyclohexane; cis-1,2-bis-perfluoro(2-phosphorus-1,3,5,7-tetramethyl-6,9,10-trioxane Cyclo [3.3.1.1 [3.7]} fluorenyl)-5-methylcyclopentane; cis-1,2-bis-(2-phospho-1, 3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4,5-dimethylcyclohexane; Formula-1,2-bis-(2-phospho-1,3,5,7-tetra(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}癸5-)-5-methylcyclopentane; and in the case where it is possible to carry out palmier isomers, it includes all of the cis-pair palmomers described above.

Other examples of substituted ligands include:- Cis-1,2-bis(di-tertiary-butylphosphinomethyl), 4,5-dimethylcyclohexane Cis-1,2-bis(di-tertiary-butylphosphinomethyl), 1,2,4,5-tetramethylcyclohexane Cis-1,2-bis(di-tertiary-butylphosphinomethyl), 3,6-diphenyl-4,5-dimethyl-cyclohexane Cis-1,2-bis(di-tertiary-butylphosphinomethyl)-5-methylcyclohexane Cis-1,2-bis(di-tertiary-butyl(phosphinomethyl)-4,5-diphenylcyclohexane Cis-5,6-bis(di-t-butylphosphinomethyl)-1,3-bis(trimethyldecyl)-3a,4,5,6,7,7a-hexahydro- 1,3H-isobenzofuran.

In yet another specific embodiment, the ligand L is a bidentate ligand of the formula (V) Wherein: A and B are as defined in formula (IV); R represents a hydrocarbyl aromatic structure having at least one aromatic ring, and Q ¹ and Q ² are each bonded to the ring via an individual linking group, at least one The aromatic ring may be on an adjacent ring atom, and the ring system is substituted on one or more of the other aromatic ring atoms by one or more substituents Y ^x ; wherein the substitution in the aromatic structure The base Y ^x has a total number of atoms other than hydrogen X = 1 - n Σ tY ^x such that X = 1 - n ΣtY ^x ≧ 4, where n is the total number of substituents Y ^x and tY ^{x is} represented on the specific substituent Y ^x The total number of atoms other than hydrogen; the groups X ¹ , X ² , X ³ and X ⁴ are as defined in formula (IV); and both Q ¹ and Q ² are as defined in formula (IV).

The novel bidentate ligands described above have been found to have surprisingly improved stability in the carbonylation reaction. Typically, the number of conversions (TON) for the carbonylation reaction, especially the hydroxy- or alkoxy-carbonylation (the number of moles of the metal/the number of moles of the product), is close to or greater than the reaction under the same conditions. The conversion number of 1,3-bis(di-tert-butylphosphino)propane is more preferably greater than that of 1,2-bis(di-tert-butylphosphinomethyl)benzene which is reacted under the same conditions. . Such conditions are preferably in a continuous reaction, but batch reactions will also benefit.

Typically, when there is more than one substituent Y ^x , it will hereinafter be referred to simply as Y, and any two may be on the same or different aromatic ring atoms of the aromatic structure. Preferably, there are 10 Y groups, meaning n is from 1 to 10, more preferably from 1 to 6 Y groups, most preferably from 1 to 4 Y groups, in the aromatic structure, and especially It is 1, 2 or 3 substituent Y groups on the aromatic structure. The substituted cyclic aromatic atom may be carbon or a hetero group, but is preferably carbon.

X = 1 - n Σ tY ^{x is} preferably between 4 and 100, more preferably 4 to 60, most preferably 4 to 20, especially 4 to 12.

Preferably, when there is a substituent Y, Y represents a group which is at least sterically hindered like a phenyl group, and when there are two or more substituents Y, each of which is like a phenyl group. Stereo sterically hindered, and/or combined to form a group that is more sterically hindered than the phenyl group.

The term "stereo-resistance" as used herein, regardless of the group R ¹ -R ¹² or the substituent Y described hereinafter, means that the term is as immediately apparent to those skilled in the art, but to avoid Any doubt that the term sterically hindered than phenyl can be taken to mean that when PH ₂ Y (representing the group Y) is reacted with Ni(0)(CO) ₄ in an eight-fold excess according to the following conditions, Has a lower degree of substitution (DS) than PH ₂ Ph. Similarly, the reference to more steric hindrance than the third-butyl group can be taken as a reference to the DS value compared to PH ₂ t-Bu and the like. If two Y groups are being compared and PHY ^{1 is} not more sterically hindered than the reference, then PHY ¹ Y ² should be compared to the reference. Similarly, if three Y groups are being compared and PHY ¹ or PHY ¹ Y ² has not been determined to be more sterically hindered than the standard, then PY ¹ Y ² Y ³ should be compared. If there are more than three Y groups, they should be taken to be more sterically hindered than the third-butyl group.

For the purposes of the present invention, the steric hindrance is discussed in CMasters "Homogeneous Transition Metal Catalysis - A Mild Technique", published by Chapman and Hall, 1981, page 14 et seq.

Tolman ("The exchange of equilibrium with phosphorus ligands on zero-valent nickel. The main role of stereochemistry", Journal of the American Chemical Society, 92, 1970, 2956-2965) has been inferred to primarily determine the stability of Ni(O) complexes. The nature of the ligand is its size, not its electronic properties.

To determine the relative steric hindrance of the group Y, the Tolman method for determining DS can be used on the phosphorus analog of the group to be determined as described above.

The Ni(CO) ₄ solution in toluene was treated with an eight-fold excess of the phosphorus ligand; the CO substitution by the ligand was followed by carbonyl stretching vibration in the infrared spectrum. The solution was allowed to equilibrate in a sealed tube by heating at 100° for 64 hours. Further heating at 100 ° for 74 hours did not significantly change the spectrum. Then, the frequency and intensity of the carbonyl stretching band in the spectrum of the equilibrium solution reached were determined. The degree of substitution can be estimated semi-quantitatively from the relative intensity, and it is assumed that the extinction coefficients of the bands are all of the same order of magnitude. For example, in the case of P (C ₆ H _{11) 3} of the, Ni (CO) ₃ L of A ₁ and ₂ L B ₂ band of _a band-based Ni (CO) having about the same intensity, it is estimated that a degree of substitution 1.5. If this experiment fails to distinguish individual ligands, diphenylphosphorus PPh ₂ H or di-tertiary-butylphosphine should be compared to PY ₂ H equivalents as appropriate. Furthermore, if it is also unable to distinguish the ligand, the PPh ₃ or P( ^t Bu) ₃ ligand should be compared with PY ₃ as appropriate. Such further experiments may require a complete replacement of the small ligand of the Ni(CO) ₄ complex.

The group Y can also be defined by reference to its cone angle, which, in the context of the invention, can be defined as the apex angle of a cylindrical cone centered at the midpoint of the aromatic ring. By midpoint is meant the point equidistant from the annular ring atoms in the plane of the ring.

The sum of the cone angles of at least one group Y, or the cone angles of two or more Y groups, is preferably at least 10, more preferably at least 20, and most preferably at least 30. The angle of the cone should be measured according to the method of Tolman {C.A. Tolman Chem. Rev. 77, (1977), 313-348}, except that the apex angle of the cone is now centered on the midpoint of the aromatic ring. This modified use of the Tolman cone angle has been used in other systems to measure steric effects, such as in cyclopentadienyl zirconium ethylene polymerization catalysts (Journal of Molecular Catalysis: Chemistry 188, (2002), 105-113).

Substituent Y is selected to be suitably sized to provide steric hindrance with respect to the active position between the Q ¹ and Q ² atoms. However, it is not known whether the substituent will prevent the metal from leaving, directing it into the pathway, generally providing a more stable catalytic confirmation, or otherwise acting.

When Y represents -SR ⁹⁰ R ⁹¹ R ⁹² , wherein S represents Si, C, N, S, O or an aryl group, and R ⁹⁰ R ⁹¹ R ⁹² is as defined later, a particularly good ligand is found. Preferably, each Y and/or a combination of two or more Y groups is at least sterically hindered as at least a third-butyl group.

More preferably, when there is only one substituent Y, it is at least sterically hindered like a third-butyl group, but in the case of two or more substituents Y, if it is regarded as a single group , each of which has a steric hindrance at least as a phenyl group, and at least has a steric hindrance as a third-butyl group.

When S is aryl, R ⁹⁰ , R ⁹¹ and R ^{92 are} preferably independently hydrogen, alkyl, -BQ ³ -X ³ (X ⁴ ) (wherein B, X ³ and X ⁴ are as defined herein, and Q ³ is as defined above for Q ¹ or Q ² ), phosphorus, aryl, arylene, alkaryl, arylenealkyl, alkenyl, alkynyl, het, hetero, halo, cyano, Nitro, -OR ¹⁹ , -OC(O)R ²⁰ , -C(O)R ²¹ , -C(O)OR ²² , -N(R ²³ )R ²⁴ , -C(O)N(R ²⁵ ) R ²⁶ , -SR ²⁹ , -C(O)SR ³⁰ , -C(S)N(R ²⁷ )R ²⁸ , -CF ₃ , -SiR ⁷¹ R ⁷² R ⁷³ or alkylphosphine.

R ¹⁹ -R ³⁰ as referred to herein may be independently and generally selected from hydrogen, unsubstituted or substituted aryl or unsubstituted or substituted alkyl, and further, R ²¹ may be nitro, halo. Base, amine or thio group.

When S is Si, C, N, S or O, R ⁹⁰ , R ⁹¹ and R ^{92 are} preferably independently hydrogen, alkyl, phosphorus, aryl, arylene, alkaryl, aralkyl, sub. Arylalkyl, alkenyl, alkynyl, het, hetero, halo, cyano, nitro, -OR ¹⁹ , -OC(O)R ²⁰ , -C(O)R ²¹ , -C(O) OR ²² , -N(R ²³ )R ²⁴ , -C(O)N(R ²⁵ )R ²⁶ , -SR ²⁹ , -C(O)SR ³⁰ , -C(S)N(R ²⁷ )R ²⁸ , -CF ₃ , -SiR ⁷¹ R ⁷² R ⁷³ or an alkylphosphine, wherein at least one of R ⁹⁰ -R ⁹² is not hydrogen, and wherein R ¹⁹ -R ³⁰ are as defined herein; and R ⁷¹ -R ⁷³ are as R ^90- R ⁹² is defined, but is preferably C ₁ -C ₄ alkyl or phenyl.

S is preferably Si, C or an aryl group. However, N, S or O may also be preferred as one or more Y groups, either in combination or in the case of a plurality of Y groups. For the avoidance of doubt, since oxygen or sulfur may be divalent, R ⁹⁰ -R ⁹² may also be unshared pairs.

In addition to the group Y, the aromatic structure may preferably be unsubstituted or, if possible, further substituted by a group selected from Y (on a non-aromatic ring atom), an alkyl group, an aryl group, a secondary aryl group, an alkylaryl group, an aralkyl group, a arylene group, an alkenyl group, an alkynyl group, a het, a hetero group, a halogen group, a cyano group, a nitro group, -OR ¹⁹ , -OC(O)R ²⁰ , -C(O)R ²¹ , -C(O)OR ²² , -N(R ²³ )R ²⁴ , -C(O)N(R ²⁵ )R ²⁶ , -SR ²⁹ , -C(O)SR ³⁰ , -C(S)N(R ²⁷ )R ²⁸ , -CF ₃ , -SiR ⁷¹ R ⁷² R ⁷³ or alkylphosphorus, wherein R ¹⁹ -R ³⁰ are as defined herein, and in Y or Y in accordance with the first aspect In the case of a defined group, the linkage is an acyclic aromatic atom to the aromatic structure; and R ⁷¹ -R ⁷³ is as defined for R ⁹⁰ -R ⁹² , but preferably a C ₁ -C ₄ alkyl group. Or phenyl. Furthermore, the at least one aromatic ring may be part of a metal alkadiene yttrium complex, for example, when R is a cyclopentadienyl or fluorenyl anion, it may form part of a metal complex. For example, dicyclopentadienyl iron, dicyclopentadienyl fluorenyl, dicyclopentadienyl molybdenum or fluorenyl equivalent.

In the context of the present invention, such a complex should be considered to be an aromatic structure, so when it contains more than one aromatic ring, the substituent Y ^x may be the same as those bonded to the Q ¹ and Q ² atoms. A family ring or other aromatic ring of this structure. For example, in the case of a metal alkadienyl hydrazide, the substituent Y ^x may be on one or more rings of the metal alkyne diene structure, and it may be the same or different from the ring to which Q ¹ and Q ² are attached.

Suitable metal alkadienium type ligands which may be substituted by a group Y as defined herein are known to the skilled person and are broadly defined in WO 04/024322. A particularly preferred Y substituent for such an aromatic anion is when S is Si.

However, in general, when S is an aryl group, the aryl group may be further unsubstituted or substituted by any other substituent defined by the above aromatic structure except for R ⁹⁰ , R ⁹¹ and R ⁹² . .

More preferred Y substituents in the present invention may be selected from the group consisting of a third-alkyl or a third-alkylaryl group such as -tri-butyl or 2-phenylpropan-2-yl, -SiMe ₃ ,- Phenyl, alkylphenyl-, phenylalkyl-, or phosphinoalkyl-, such as phosphinomethyl.

When S is Si or C, and one or more of R ⁹⁰ -R ⁹² are hydrogen, at least one of R ⁹⁰ -R ⁹² is preferably sufficiently bulky to obtain the desired steric hindrance, and such a group Preference is given to phosphorus, phosphinoalkyl-, groups having a tertiary carbon, such as a -tri-butyl, -aryl, -alkylaryl, -aralkyl or tertiary alkylene group.

The hydrocarbyl aromatic structure preferably has (including a substituent) 5 to up to 70 ring atoms, more preferably 5 to 40 ring atoms, most preferably 5 to 22 ring atoms, especially if the non-metal alkadiene is wrong. The compound is 5 or 6 ring atoms.

The aromatic hydrocarbon group structure may preferably be monocyclic or polycyclic. The cyclic aromatic atom may be a carbon or a hetero group, and the reference to a hetero group herein refers to sulfur, oxygen and/or nitrogen. However, it is preferred that the Q ¹ and Q ² atoms are bonded to the at least one aromatic ring to adopt adjacent ring carbon atoms. Typically, when the cyclic hydrocarbon group structure is polycyclic, it is preferably bicyclic or tricyclic. The other rings in the aromatic structure may or may not be aromatic in nature, and the aromatic structure should be understood accordingly. A non-aromatic cyclic ring as defined herein may comprise an unsaturated bond. The ring atom system means an atom forming a cyclic skeleton portion.

Preferably, the bridging group -R(Y ^X ) _n , whether further substituted, or preferably contains less than 200 atoms, more preferably less than 150 atoms, more preferably less than 100 atom.

The term "one other aromatic ring atom of an aromatic structure" means any other aromatic ring atom in the aromatic structure which is not at least one aromatic ring to which the Q ¹ or Q ² atom is bonded via a linking group. It is possible to use adjacent ring atoms.

As mentioned above, the immediately adjacent ring atoms on either side of the adjacent ring atoms may preferably be unsubstituted. As the following examples, the position of the ring via an atom bonded to Q ^1, and the aromatic phenyl ring via the position ² of the ring atoms bonded to the 2 Q, one preferred system having substituent on the ring positions 4 and 5 or A plurality of such other aromatic ring atoms, and two substituents which are not substituted at positions 3 and 6, may employ adjacent ring atoms immediately adjacent to each other. However, this is only a preferred substituent arrangement, and substitutions such as at ring positions 3 and 6 are possible.

The term aromatic ring means that at least one ring to which Q ¹ and Q ² atoms are individually bonded via B and A is aromatic, and aromatic is preferably interpreted broadly to include not only phenyl or cyclopentadienyl. Anionic, pyrrolyl, pyridyl type structures, and other rings having aromaticity, such as found in any ring having delocalized π electrons that are free to move in the ring.

Preferably, the aromatic ring system has 5 or 6 atoms in the ring, but a ring having 4n + 2 π electrons is also possible, such as [14] hepene, [18] hepene and the like.

The aromatic hydrocarbon group structure may be selected from 4 and/or 5 tert-alkylbenzene-1,2-diyl, 4,5-diphenyl-benzene-1,2-diyl, 4 and/or 5-benzene Base-benzene-1,2-diyl, 4,5-di-t-butyl-benzene-1,2-diyl, 4 or 5-tri-butylbenzene-1,2-diyl, 2,3,4 and/or 5th-alkyl-naphthalene-8,9-diyl, 1H-indole-5,6-diyl, 1,2 and/or 3 methyl-1H-indole-5 ,6-diyl, 4,7-methylalkyl-1H-indole-1,2-diyl, 1,2 and/or 3-dimethyl-1H-indole-5,6-diyl, 1,3 - bis(trimethyldecyl)-isobenzofuran-5,6-diyl, 4-(trimethyldecyl)benzene-1,2-diyl, 4-phosphinotoluene-1,2- Diyl, 4-(2'-phenylpropan-2'-yl)benzene-1,2-diyl, 4-dimethylnonanylbenzene-1,2-diyl, 4-di-third- Butyl, methyl decyl benzene-1,2-diyl, 4-(t-butyldimethyl decyl)-benzene-1,2-diyl, 4-tri-butyl decyl- Benzene-1,2-diyl, 4-(tri-tert-butyl-decyl)-benzene-1,2-diyl, 4-(2'-tris-butylpropan-2'-yl) Benzene-1,2- Base, 4-(2',2',3',4',4'-pentamethyl-penta-3'-yl)-benzene-1,2-diyl, 4-(2',2', 4',4'-Tetramethyl-3'-tris-butyl-penta-3'-yl)-benzene-1,2-diyl, 4-(or 1')tri-alkyl bicyclic Pentadiene iron-1,2-diyl, 4,5-diphenyl-dicyclopentadienyl iron-1,2-diyl, 4-(or 1')phenyl-dicyclopentadienyl iron -1,2-diyl, 4,5-di-tertiary-butyl-dicyclopentadienyl iron-1,2-diyl, 4-(or 1') tert-butyldicyclopentane Allyl-1,2-diyl, 4-(or 1')(trimethyldecyl)dicyclopentadienyl iron-1,2-diyl, 4-(or 1')phosphinomethyldi Cyclopentadienyl iron-1,2-diyl, 4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron-1,2-diyl, 4-( Or 1') dimethyl decyl dicyclopentadienyl iron-1,2-diyl, 4-(or 1') di-tertiary-butyl, methyl decyl dicyclopentadienyl iron-1 ,2-diyl, 4-(or 1')(tris-butyldimethylmethylalkyl)-dicyclopentadienyl iron-1,2-diyl, 4-(or 1') third- Butyl decyl-dicyclopentadienyl iron-1,2-diyl, 4-(or 1') (three Tertiary-butyl decyl)-dicyclopentadienyl iron-1,2-diyl, 4-(or 1')(2'-tris-butylpropan-2'-yl)dicyclopentane Allyl-1,2-diyl, 4-(or 1')(2',2',3',4',4'pentamethyl-penta-3'-yl)-dicyclopentadienyl iron -1,2-diyl, 4-(or 1')(2',2',4',4'-tetramethyl-3'-tris-butyl-pentyl-3'-yl)-di Cyclopentadienyl iron-1,2-diyl.

As mentioned above, in some embodiments, there may be two or more Y and/or non-Y substituents on other aromatic ring atoms of the aromatic structure. The two or more substituents may be combined as appropriate to form other ring structures, such as cycloaliphatic ring structures, especially when adjacent to a cyclic aromatic atom.

Such cycloaliphatic ring structures may be saturated or unsaturated, bridged or unbridged, and are alkyl, Y group, aryl, arylene, alkaryl, aralkyl, aralkyl, as defined herein. Base, alkenyl, alkynyl, het, hetero, halo, cyano, nitro, -OR ¹⁹ , -OC(O)R ²⁰ , -C(O)R ²¹ , -C(O)OR ²² , -N(R ²³ )R ²⁴ , -C(O)N(R ²⁵ )R ²⁶ , -SR ²⁹ , -C(O)SR ³⁰ , -C(S)N(R ²⁷ )R ²⁸ , -CF ₃ , -SiR ⁷¹ R ⁷² R ⁷³ or a phosphinoalkyl group, wherein when present, at least one of R ⁹⁰ -R ⁹² is not hydrogen, and wherein R ¹⁹ -R ³⁰ are as defined herein; and R ⁷¹ -R ⁷³ Is as defined for R ⁹⁰ -R ⁹² , but preferably C ₁ -C ₄ alkyl or phenyl, and/or one or more (preferably less than a total of 4) oxygen, nitrogen, sulfur, cesium The atom is either inserted by a decyl or dialkyl fluorenyl group, or a mixture thereof.

Examples of such structures include hexahydropyridine, pyridine, morpholine, cyclohexane, cycloheptane, cyclooctane, cyclodecane, furan, dioxane, alkyl substituted DIOP, 2-alkyl substitution. 1,3 dioxane, cyclopentanone, cyclohexanone, cyclopentene, cyclohexene, cyclohexadiene, 1,4 dithiolyl, hexahydropyridyl , tetrahydropyrrole, thiomorpholine, cyclohexenone, bicyclo[4.2.0]octane, bicyclo[4.3.0]nonane, adamantane, tetrahydropyran, dihydropyran, tetra Hydrothiopyran, tetrahydro-furan-2-one, δ valerolactone, γ-butyrolactone, glutaric anhydride, dihydroimidazole, triazacyclononane, triazacyclononane, thiazole, six Hydrogen-1H-indole (5,6-diyl), octahydro-4,7-methylalkyl-indole (1,2-diyl) and tetrahydro-1H-indole (5,6-diyl), All may be unsubstituted or substituted as defined herein for aryl.

However, neither form of combined groups or otherwise, preferred is that Q ¹ in the immediately preceding atom to any side of the ring and Q ² can be linked through the linking group of adjacent adjacent the aromatic The ring atomic system is less preferentially substituted, and when the aromatic structure contains more than one aromatic ring, it is preferred that the substituent is elsewhere on the at least one aromatic ring, or elsewhere in the aromatic structure, and This is a preferred location for combining the Y substituents.

In the above formulae 1a and 1b representing the groups X ³ and X ⁴ or X ¹ and X ² accompanied by a Q ¹ or Q ² atom, the group Y ¹ or Y ² should be individually grouped by the group YY ¹ or YY ² Replace.

YY ¹ and YY ² , when present, each independently represent oxygen, sulfur or N-R ⁵⁵ , wherein R ⁵⁵ represents hydrogen, alkyl or aryl.

In the present invention, the particularly preferred combination of Formula V includes the following, wherein: -(1)X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), X ¹ represents CR ¹ (R ² )(R ³ ), and X ² represents CR ⁴ (R ⁵ )(R ⁶ ); A and B are the same, and represent —CH ₂ —; both Q ¹ and Q ² represent Phosphorus, linked to the R group at ring positions 1 and 2; R represents 4-(trimethyldecyl)-benzene-1,2-diyl.

(2) X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), X ¹ represents CR ¹ (R ² )(R ³ ), and X ² represents CR ⁴ (R ⁵ )(R ⁶ ); A and B are the same and represent -CH ₂ -; both Q ¹ and Q ² represent phosphorus, which is bonded to the R group at ring positions 1 and 2; R represents 4-Terti-butyl-benzene-1,2-diyl.

⁽³⁾ X 3 X ⁴ are attached to the Q ¹ and their together form a 2-phospha - adamantyl, and form a 2 X ^{1 2} X ² and P together with their attached the Q - alkoxy magic A; A and B are the same and represent -CH ₂ -; both Q ¹ and Q ² represent phosphorus, linked to the R group at ring positions 1 and 2; R represents 4-(trimethyldecylalkyl) )-Benzene-1,2-diyl.

(4) X ¹ , X ² , X ³ and X ⁴ represent a gold steel alkyl group; A and B are the same and represent -CH ₂ -; both Q ¹ and Q ² represent phosphorus, which is linked to the ring position 1 And the R group on 2; R represents 4-(trimethyldecyl)-benzene-1,2-diyl.

Particularly preferred compounds of the formula V include the following, wherein: each of R ¹ to R ¹² is the same and represents a methyl group; A and B are the same and represent -CH ₂ -; and R represents 4-tert-butyl-benzene. -1,2-diyl or 4-(trimethyldecyl)-benzene-1,2-diyl.

Examples of suitable bidentate ligands are 1,2-bis(di-t-butyl-butylphosphinomethyl)-4,5-diphenylbenzene; 1,2-bis(di-third-butyl) , phosphinylmethyl)-4-phenylbenzene; 1,2-bis(di-tertiary-butylphosphinomethyl)-4,5-bis-(trimethyldecyl)benzene; 1,2 - bis(di-t-butylphosphinomethyl)-4-(trimethyldecyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl Base-6,9,10-trioxy-gold steel alkyl)-4,5-diphenylbenzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl -6,9,10-trioxy-gold steel alkyl)-4-phenylbenzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9 , 10-trioxo-gold steel alkyl)-4,5-bis-(trimethyldecyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl Base-6,9,10-trioxy-gold steel alkyl)-4-(trimethyldecyl)benzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5- Diphenylbenzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4-phenylbenzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5 - bis-(trimethyldecyl)benzene; 1,2-bis(di-gold) Steel alkylphosphinomethyl)-4-(trimethyldecyl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-third- Butylphosphinomethyl)-4,5-diphenylbenzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-tertiary-butylphosphine Methyl)-4-phenylbenzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl)-4 , 5-bis-(trimethyldecyl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-tertiary-butylphosphinomethyl) )-4-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)- 2-(di-tert-butylphosphinomethyl) 4,5-diphenylbenzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9, 10-trioxo-gold steel alkyl)-2-(di-t-butylphosphinomethyl)-4-phenylbenzene; 1-(2-phosphinomethyl-1,3,5,7 -tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl)-4,5-bis-(trimethyldecyl)benzene ;1-(2-phospho-based Base-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4-(trimethyl) Benzyl)benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold steel alkyl)-2-(di-gold lanthanane Phosphinylmethyl)-4,5-diphenylbenzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold lanthanane Base-2-(di-gold-steel alkylphosphinomethyl)-4-phenylbenzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10 -trioxo-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4,5-bis-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1 ,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl)-4-(trimethyldecyl)benzene ; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-diphenylbenzene; 1-(di-tertiary-butyl Phosphylmethyl)-2-(di-gold-steel alkylphosphinomethyl)-4-phenylbenzene; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkyl Phosphylmethyl)-4,5-bis-(trimethylhydrazine Benzo; phenyl; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4-(trimethyldecyl)benzene; 1,2-double (2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4,5-diphenylbenzene ; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4- Phenylbenzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]} mercapto) -4,5-bis-(trimethyldecyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxacyclohexane -{3.3.1.1[3.7]} mercapto)-4-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10- Trioxocyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)-4,5-diphenylbenzene; 1-(2-phosphino group Methyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphino) 4-phenylbenzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxane And -{3.3.1.1[3.7]} mercapto)-2-(di-t-butylphosphinomethyl)-4,5-bis-(trimethyldecyl)benzene; 1-(2- Phosphylmethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphine) Methyl)-4-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3 .1.1[3.7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-diphenylbenzene; 1-(2-phosphinomethyl-1,3,5-tri Methyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-phenylbenzene; 1-( 2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphine Methyl)-4,5-bis-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxane And -{3.3.1.1[3.7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-(trimethyldecyl)benzene; 1,2-bis-perfluoro(2- Phosphylmethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[ 3.7]}-mercapto)-4,5-diphenylbenzene; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10 - trioxane and {3.3.1.1[3.7]}mercapto)-4-phenylbenzene; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl Base-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}-mercapto)-4,5-bis-(trimethyldecyl)benzene; 1,2-bis-perfluoro 2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4-(trimethyldecyl) Benzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[ 3.7]} mercapto)-4,5-diphenylbenzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl)-6,9 , 10-trioxane and {3.3.1.1[3.7]}mercapto)-4-phenylbenzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra Trifluoro-methyl)-6,9,10-trioxatricyclo{3.3.1.1[3.7]}mercapto)-4,5-bis-(trimethyldecyl)benzene; 1,2-double -(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}decyl)-4 -(trimethyldecylalkyl) Benzene; 1,2-bis(di-t-butylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1,2-bis(di) -T-butylphosphinomethyl)-4-(2'-phenylpropan-2'-yl)benzene; 1,2-bis(di-t-butylphosphinomethyl)-4, 5-di-tert-butylbenzene; 1,2-bis(di-t-butyl-butylphosphinomethyl)-4-tris-butylbenzene; 1,2-bis(2-phosphino) Base-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4-(2'-phenylpropane- 2'-yl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4,5 -(di-tert-butyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl -4-tri-butylbenzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4-(2'-phenylpropan-2'-yl)benzene; 1,2-double (two - gold steel alkylphosphinomethyl)-4,5-(di-tert-butyl)benzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4-third-butyl Benzobenzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl)-4,5-di-(2' -Phenylpropan-2'-yl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl)- 4-(2'-phenylpropan-2'-yl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphine) Methyl)-4,5-(di-tert-butyl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-third- Butylphosphinomethyl)-4-tri-butylbenzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel Alkyl)-2-(di-tertiary-butylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1-(2-phosphinomethyl -1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl)-4-(2'- Phenylpropan-2'-yl)benzene; 1-(2-phosphine Methyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl) 4,5-( Di-t-butyl)benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-( Di-t-butylphosphinomethyl)-4-tri-butylbenzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10- Tris-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1-(2-phosphine Methyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl)-4-(2' -Phenylpropan-2'-yl)benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2 -(二金钢alkylphosphinomethyl)-4,5-(di-tertiary-butyl)benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl- 6,9,10-trioxy-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4-tri-butylbenzene; 1-(di-tertiary-butylphosphino Methyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropane 2'-yl)benzene; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4-(2'-phenylpropan-2'- Benzene; 1-(di-tertiary-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-(di-tertiary-butyl)benzene; -(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4-tri-butylbenzene; 1,2-bis(2-phosphinomethyl -1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4,5-di-(2'-phenylpropane-2 '-yl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}癸4-(2'-phenylpropan-2'-yl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-tri Oxytricyclo-{3.3.1.1[3.7]}mercapto)-4,5-(di-tert-butyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5 -trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4-tri-butylbenzene; 1-(2-phosphinomethyl-1, 3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di- -butylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl- 6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)-4-(2'-phenylpropane- 2'-yl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]} mercapto) -2-(di-t-butylphosphinomethyl)-4,5-(di-tert-butyl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl Group-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-tertiary-butylphosphinomethyl)-4-tri-butylbenzene ; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(two gold Steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl- 6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-(2'-phenylpropane-2' -yl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3. 1.1[3.7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-(di-tertiary-butyl)benzene; 1-(2-phosphinomethyl-1, 3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-third -butylbenzene; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1 [3.7 ]}-mercapto)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5, 7-Tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4-(2'-phenylpropan-2'-yl)benzene; 1,2- Bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}-mercapto)-4, 5-(di-tert-butyl)benzene; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxane Cyclo-{3.3.1.1[3.7]}mercapto)-4-tri-butylbenzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro- Methyl)-6,9,10-trioxatricyclo{3.3.1.1[3.7]}mercapto)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 2-double-(2 Phosphylmethyl-1,3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4-(2' -Phenylpropan-2'-yl)benzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetrakis(trifluoro-methyl)-6,9,10-tri Oxytricyclo and {3.3.1.1[3.7]} mercapto)-4,5-(di-tert-butyl)benzene; 1,2-bis-(2-phosphinomethyl-1,3,5 , 7-tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1 [3.7]} mercapto)-4-tri-butylbenzene.

An example of a suitable bidentate dicyclopentadienyl iron type ligand is 1,2-bis(di-tertiary-butylphosphinomethyl)-4,5-diphenyldicyclopentadienyl iron; 1,2-bis(di-t-butylphosphinomethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1,2-bis(di-tertiary-butylphosphino) Methyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(di-tertiary-butylphosphinomethyl)-4- (or 1') (trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel Alkyl)-4,5-diphenyldicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-tri Oxygen-gold steel alkyl) 4-(or 1')phenyl dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6, 9,10-trioxy-gold steel alkyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3, 5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl) 4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1,2-double (two -Golden steel alkylphosphinomethyl)-4,5 diphenyl di Iron pentadiene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4-(or 1')phenyl dicyclopentadienyl iron; 1,2-bis(di-gold lanthanane Phosphinylmethyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(di-gold steel alkylphosphinomethyl)-4- (or 1 ')(trimethyldecyl)dicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-tertiary-butylphosphino) Methyl)-4,5-diphenyldicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-tertiary-butyl Phosphylmethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di- Tri-butylphosphinomethyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl )-2-(di-t-butylphosphinomethyl)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1 ,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl) 4,5-diphenyl bicyclo E Alkenyl; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butyl Phosphinomethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10- Tris-gold steel alkyl)-2-(di-tert-butylphosphinomethyl) 4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphine Methyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4-( Or 1') (trimethyldecyl) dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold Steel alkyl)-2-(digold steel alkylphosphinomethyl)-4,5-diphenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7 - tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl) -4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(2- Phosphylmethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl)-4- (or 1') (trimethyldecyl) dicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5 - diphenyldicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4-(or 1')phenyl Dicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-bis-(trimethyldecyl) Dicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4-(or 1') (trimethyldecylalkyl) Dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7] }癸))-4,5-diphenyldicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxane Tricyclic-{3.3.1.1[3.7]}mercapto)-4-(or 1')phenyl dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5 -trimethyl-6,9,10-trioxatricyclo- {3.3.1.1 [3.7]} mercapto)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5 -trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di- Tri-butylphosphinomethyl)-4,5-diphenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10- Trioxocyclo-{3.3.1.1[3.7]}decyl)-2-(di-t-butylphosphinomethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di- Tri-butylphosphinomethyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl- 6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)-4-(or 1') Base alkyl) dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl- 6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-diphenyldicyclopentadiene Iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(two Gold-steel alkylphosphinomethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9, 10-trioxotricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-bis-(trimethyldecyl)dicyclopentane Diene iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2- (two gold steel alkylphosphinomethyl)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl-1 ,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}-mercapto)-4,5-diphenyldicyclopentadienyl iron; ,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}indenyl)- 4-(or 1') phenyl dicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7- Tetramethyl-6,9,10-trioxatricyclo{3.3.1.1[3.7]}-mercapto)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4 -(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl) -6,9,10-trioxatricyclo{3.3.1.1[3.7]}mercapto)-4,5-diphenyldicyclopentadienyl iron; 1,2-bis-(2-phosphino) Base-1,3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4-(or 1')benzene Iron dicyclopentadienyl; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo {3.3.1.1 [3.7]} mercapto)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis-(2-phosphinomethyl-1,3, 5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4-(or 1')(trimethyldecyl) Dicyclopentadienyl iron; 1,2-bis(di-tertiary-butylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)bicyclo Diene iron; 1,2-bis(di-t-butylphosphinomethyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(di-tert-butylphosphinomethyl)-4,5-di-tert-butyldicyclopentadienyl iron; 1,2-bis(di-tertiary-butyl Phosphylmethyl)-4-(or 1') tris-butyldicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl- 6,9,10-trioxy-gold steel alkyl)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(2-phosphine Methyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4-(or 1')(2'-phenylpropan-2'-yl Dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4, 5-(di-tert-butyl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-tri Oxygen-gold steel alkyl)-4-(or 1') tris-butyldicyclopentadienyl iron; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5-di -(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(di-gold steel alkylphosphine) Methyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(di-gold steel alkylphosphinomethyl)- 4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1,2-bis(di-gold steel alkylphosphinomethyl)-4-(or 1') tert-butyl Dicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl)-4,5-di -(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-third -butylphosphinomethyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(P,P-gold steel alkyl third - Butylphosphinomethyl)-2-(di-t-butylphosphinomethyl)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1-(P,P - Goldsteel alkyl tertiary-butylphosphinomethyl)-2-(di-tertiary-butylphosphinomethyl)-4-(or 1') tert-butyldicyclopentadiene iron ; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphino Methyl) 4,5-di-(2'-phenyl Propane-2'-yl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl) 2-(di-tertiary-butylphosphinomethyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphine Methyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl) 4,5- (di-tertiary-butyl) dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold lanthanane 2-(2-tri-butylphosphinomethyl)-4-(or 1') tris-butyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1, 3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4,5-di-(2'-benzene Propyl-2'-yl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl -2-(di-gold-steel alkylphosphinomethyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphino group Methyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(two gold steel Alkylphosphinomethyl)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl- 6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl)-4-(or 1') tert-butyldicyclopentadienyl iron; (di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentane Diene iron; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4-(or 1')(2'-phenylpropane-2 '-yl)dicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-(di-third -butyl)dicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4-(or 1') third -butyl dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[ 3.7]} mercapto)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3, 5-trimethyl-6,9,10-trioxatricyclo-{ 3.3.1.1 [3.7]} mercapto)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl) -1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4,5-(di-tri-butyl)bicyclic Iron pentadiene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]} fluorenyl -4-(or 1') tri-butyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxane Cyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl) Dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]} mercapto) 2-(di-tertiary-butylphosphinomethyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphine Methyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-tertiary-butylphosphino) Methyl)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl -6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)-4-(or 1') third -butyl dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]} Mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphine Methyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl -4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6 ,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-(di-tertiary-butyl) Dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]} mercapto) -2-(di-gold-steel alkylphosphinomethyl)-4-(or 1') tris-butyldicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl- 1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}-mercapto)-4,5- Di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl- 6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}-fluorenyl -4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl- 6,9,10-trioxotane and {3.3.1.1[3.7]}mercapto)-4-(or 1') tris-butyldicyclopentadienyl iron; 1,2-bis-(2 -phosphinomethyl-1,3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4,5- Di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-A) -6,9,10-trioxane and {3.3.1.1[3.7]}mercapto)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentane Alkene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxatriene and {3.3.1.1[ 3.7]}癸基)-4,5 (di-tertiary-butyl) dicyclopentadienyl iron; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl)-6,9 , 10-trioxane and {3.3.1.1 [3.7]} mercapto)-4-(or 1') tris-butyldicyclopentadienyl iron.

The selected structure of the ligand of the formula V of the present invention comprises:- 1,2-bis(di-tertiary-butylphosphinomethyl)-3,6-diphenyl-4,5-xylene 1,2 bis(di-tertiary-butyl(phosphinomethyl)-4,5-diphenylbenzene 1,2-bis(di-tertiary-butylphosphinomethyl)-1'-trimethyldecyl dicyclopentadiene iron 1,2-bis(di-tertiary-butylphosphinomethyl)-1'-tris-butyldicyclopentadiene iron 5,6-bis(di-t-butylphosphinomethyl)-1,3-bis-trimethyldecyl-1,3-dihydroisobenzofuran 1,2-bis(di-tertiary-butylphosphinomethyl)-3,6-diphenylbenzene 1,2-bis(di-tertiary-butylphosphinomethyl)-4-trimethyldecyl dicyclopentadiene iron 1,2 bis(di-tertiary-butyl(phosphinomethyl))-4,5-di(4'-tert-butylphenyl)benzene 1,2-bis(di-t-butyl-butyl(phosphinomethyl))-4-trimethyldecylbenzene 1,2-bis(di-tertiary-butyl(phosphinomethyl))-4-(tris-butyldimethylmethylalkyl)benzene 1,2-bis(di-tertiary-butyl(phosphinomethyl))-4,5-bis(trimethyldecyl)benzene 1,2-bis(di-t-butyl-butyl(phosphinomethyl))-4-tri-butylbenzene 1,2-bis(di-tertiary-butyl(phosphinomethyl))-4,5-di-t-butylbenzene 1,2-bis(di-tertiary-butyl(phosphinomethyl))-4-(tri-tert-butylmethyl)benzene 1,2-bis(di-tertiary-butyl(phosphinomethyl))-4-(tri-tert-butyl-decyl)benzene 1,2-bis(di-tertiary-butyl(phosphinomethyl))-4-(2'-phenylpropan-2'-yl)benzene 1,2-bis(di-tertiary-butyl(phosphinomethyl))-4-phenylbenzene 1,2-bis(di-tertiary-butyl(phosphinomethyl))-3,6-dimethyl-4,5-diphenylbenzene 1,2-bis(di-tertiary-butyl(phosphinomethyl))-3,4,5,6-tetraphenylbenzene 4-(1-{3,4-bis-[(di-t-butyl-phosphinyl)-methyl]-phenyl}-1-methyl-ethyl)-benzamide 1,2-bis(di-tertiary-butyl(phosphinomethyl)-4-(4'-chlorocarbonyl-phenyl)benzene 1,2-bis(di-tertiary-butyl(phosphinomethyl))-4-(phosphinomethyl)benzene 1,2-bis(di-tertiary-butyl(phosphinomethyl))-4-(2'-naphthylpropan-2'-yl)benzene 1,2-bis(di-tertiary-butyl(phosphinomethyl))-4-(3',4'-bis(di-tertiary-butyl(phosphinomethyl))phenyl)benzene 1,2-bis(di-tertiary-butyl(phosphinomethyl))-3-(2',3'-bis(di-tertiary-butyl(phosphinomethyl))phenyl)benzene 1,2-bis(di-tertiary-butyl(phosphinomethyl))-4-t-butyl-5-(2'-tert-butyl-4',5'-bis(di- Tri-butyl(phosphinomethyl)phenyl)benzene

In the above examples, the structure of the ligand of the formula (V), one or more groups having a X ¹ -X ⁴ tertiary carbon, a third-butyl group, linked to Q ¹ and/or Q ^{The 2} group, phosphorus, can be replaced by a suitable replacement group. Preferred alternative groups are gold steel alkyl, 1,3-dimethyl fund steel alkyl, emblem alkyl, positive Base or 1-positive A dienyl group, or X ¹ together with X ² and/or X ³ together with X ⁴ , accompanied by the phosphorus, forms a 2-phosphorus tricyclic ring [3.3.1.1{3,7} fluorenyl group, such as 2-phosphorus- 1,3,5,7-tetramethyl-6,9,10-trioxy gold steel alkyl or 2-phosphorus-1,3,5-trimethyl-6,9,10-trioxane base.

In most embodiments of formula (I)-(V), it is preferred that the X ¹ -X ⁴ group or the combined X ¹ /X ² and X ³ /X ⁴ groups or equivalent (I The groups are the same, but they may also advantageously use different groups to create asymmetry around the active sites in such selected ligands and generally in the present invention.

Q ^{2 is} preferably phosphorus, and Q ^{1 is} preferably independently phosphorus.

The bidentate ligand is preferably a bidentate phosphine, anthracene or The ligand is preferably a phosphine ligand.

The palladium complex of the present invention can be used as a precatalyst for the carbonylation of ethylenically unsaturated compounds. A suitable ethylenically unsaturated compound of the non-ethylene specific aspect of the present invention is an ethylenically unsaturated compound having 2 to 50 carbon atoms per molecule, or a mixture thereof. Suitable ethylenically unsaturated compounds may have one or more isolated or conjugated unsaturated bonds per molecule. Preferred are compounds having 2 to 20 carbon atoms or mixtures thereof, more preferably compounds having up to 18 carbon atoms, more preferably up to 16 carbon atoms, and more preferably more than 10 compounds. One carbon atom. The ethylenically unsaturated compound may further contain a functional group or a hetero atom such as nitrogen, sulfur or an oxide. Examples include carboxylic acids, esters or nitriles as functional groups. In a preferred embodiment, the ethylenically unsaturated compound is a mixture of olefins or olefins. Such olefins can be converted via reaction with carbon monoxide and, where appropriate, a linear carbonylation product with a high regioselective co-reactant. Suitable ethylenically unsaturated compounds include acetylene, methyl acetylene, propyl acetylene, butadiene, ethylene, propylene, butylene, isobutylene, pentene, pentenenitrile, alkyl pentenoates, such as 3-pentene Methyl esters, pentenoic acids (such as 2- and 3-pentenoic acid), vinyl acetate, octenes.

Particularly preferred ethylenically unsaturated compounds are ethylene, vinyl acetate, butadiene, pentenoic acid alkyl esters, pentenenitriles, pentenoic acids (such as 3-pentenoic acid), acetylene and propylene.

Particularly preferred are ethylene, vinyl acetate, butadiene and pentenenitriles.

The metal complex production reaction is preferably carried out at a temperature in the range of from 20 ° C to 120 ° C, more preferably from 20 ° C to 90 ° C, especially from 50 ° C to 80 ° C. The reaction temperature is preferably kept below the decomposition temperature, so that when the metal phosphine is known to decompose within the temperature range given above, the reaction temperature should be maintained at least 10 ° C (and preferably at least 20 ° C) lower than The decomposition temperature.

In the manufacture of metal complexes, the miscible compound is preferably present in the reaction mixture in a stoichiometric excess. The amount of the miscible compound in the reaction mixture is preferably calculated to provide at least 10% molar excess, more preferably at least 50% excess, especially at least 90%, in excess of the amount required for the stoichiometric reaction. When the ligand L is a phosphine, it is preferred to use a 10-25% excess of the phosphine. When palladium is reduced in the formation of the product palladium complex, this reduction can be achieved by a miscible compound, and some excess of the miscible compound is preferably used in the reaction mixture to achieve this reduction.

The metal complex production reaction can be carried out in the presence of a solvent. When water is used as the solvent, the pH of the solution can be controlled. The concentration of the metal amination in the solvent is preferably from 5 to 25 grams of Pd per liter of solution. The pH of the reaction mixture is preferably adjusted and maintained in the range of 2 to 7. A buffer solution can be added to the reaction mixture. Alternative solvents include alcohols (e.g., methanol, ethanol, propanol, denatured alcohol), acetonitrile, tetrahydrofuran, toluene, aliphatic esters such as ethyl acetate, and ketones such as methyl ethyl ketone. When the compound is a phosphine, an organic solvent is required.

The reactants may be added in any suitable order, but in a preferred method of the invention, the metal amide is placed in a reaction vessel with solvent (if used), base (if used), and buffer solution (if used) Time), if necessary, heat, then add the compound.

The reaction can last from 30 minutes to several hours, but is usually completed in about four hours. Upon completion, the product metal complex is separated from the reaction mixture by any suitable method depending on the physical form of the product.

The catalyst system of the present invention can be used homogeneously or heterogeneously. This catalyst system is preferably used homogeneously.

In the case where the compound of the formula herein contains an alkenyl or cycloalkyl moiety as defined, cis (E) and trans (Z) isomerism may also occur. The invention includes individual stereoisomers of any of the formulae compounds as defined herein, and, where appropriate, individual tautomeric forms thereof, as well as mixtures thereof. The separation of diastereomers or cis and trans isomers can be achieved by conventional techniques, for example by fractional crystallization of a mixture of stereoisomers of one of the formulae or a suitable salt or derivative thereof. Analysis or HPLC. The individual palmomers of one of the compounds of the formula may also be prepared from the corresponding optically pure intermediates, or by resolution, such as by using an appropriate pair of palmitic carriers, by HPLC of their corresponding racemates, or by Fractional crystallization of diastereomeric salts formed by reaction of their corresponding racemates with a suitable optically active acid or base, in a suitable manner.

All stereoisomers are included within the scope of the methods of the invention.

It will be apparent to those skilled in the art that the compounds of formula (I)-(V) can act as ligands which will coordinate with Group 8, 9 or 10 metals or their compounds to form compounds for use in the present invention. In the invention. Typically, the Group 8, 9 or 10 metal or compound thereof is coordinated to one or more of the phosphorus, arsenic and/or antimony atoms of the compound of formula (I).

As mentioned above, the present invention provides a process for the carbonylation of an ethylenically unsaturated compound which comprises reacting an ethylenically unsaturated compound in the presence of a catalyst compound as defined in the present invention with carbon monoxide. It is contacted with a source of a hydroxyl group such as water or an alkanol.

Suitably, the source of the hydroxyl group comprises an organic molecule having a hydroxyl functional group. The organic molecule having a hydroxy functional group may preferably be branched or linear, and includes an alkanol, particularly a C ₁ -C ₃₀ alkanol, including an aryl alkanol, which may optionally be substituted with one or more substituents, The substituent is selected from the group consisting of alkyl, aryl, Het, halo, cyano, nitro, OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , C(S)R ²⁷ R ²⁸ , SR ²⁹ or C(O)SR ³⁰ , as defined herein. Highly preferred alkanols are C ₁ -C ₈ alkanols such as methanol, ethanol, propanol, isopropanol, isobutanol, tert-butanol, n-butanol, phenol and chlorodecyl alcohol. Although monoalkanols are preferred, polyalkanols may also be utilized, preferably selected from the group consisting of di- and octanols such as glycols, triols, tetrols, and sugars. Typically, such polyalkanols are selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, glycerin, 1,2,4-butanetriol, 2-(hydroxymethyl)-1,3- Propylene glycol, 1,2,6-trihydroxyhexane, pentaerythritol, 1,1,1-tris(hydroxymethyl)ethane, sucrose, sucrose, galactose, and other saccharides. Preferred sugars include sucrose, fructose and glucose. The particularly preferred alkanols are methanol and ethanol. The preferred alkanol is methanol.

The amount of alcohol is not important. In general, the amount used is greater than the mass to be carbonylated. Therefore, the alcohol can also be used as a reaction solvent, and if necessary, individual solvents can also be used.

It should be understood that the final product of the reaction is at least partially determined by the source of the alkanol used. For example, the use of methanol produces its corresponding methyl ester. Conversely, the use of water produces its corresponding acid. Accordingly, the present invention provides a convenient method for the addition of a group -C(O)OC ₁ -C ₃₀ alkyl or aryl or -C(O)OH over an ethylenically unsaturated bond.

In the process according to the second aspect of the invention, the carbon monoxide may be used neat or diluted with an inert gas such as nitrogen, carbon dioxide, or a rare gas such as argon. A small amount of hydrogen, typically less than 5% by volume, may also be present.

In the liquid reaction medium, the ratio (volume/volume) of the ethylenically unsaturated compound to the hydroxyl source may vary over a wide range, and suitably ranges from 1:0.1 to 1:10, preferably 2 Between 1 and 1:2, and up to a large excess of alkanol or water, when the latter is also a reaction solvent, such as up to 100:1 excess of alkanol or water. However, if the ethylenically unsaturated compound is a gas at the reaction temperature, it may be present in the liquid phase reaction medium at a lower content, for example, in the ratio of the source of the hydroxyl group of 1:20,000 to 1:10, more preferably It is 1:10,000 to 1:50, preferably 1:5000 to 1:500.

The amount of the catalyst of the present invention used in the carbonylation process is not critical. When the amount of the Group 8, 9 or 10 metal in the liquid phase carbonylation reaction medium is preferably in the range of 10 ^-7 to 10 ^-1 per mol of the ethylenically unsaturated compound, more preferably 10 ^-6 to 10 ^-2 , the best is 10 ^-5 to 10 ^-2 moles, good results are obtained.

Suitably, although not essential to the invention, the carbonylation of the ethylenically unsaturated compound as defined herein may be carried out in one or more aprotic solvents. Suitable solvents include ketones such as methyl butyl ketone; ethers such as toluene ether (methyl phenyl ether), 2,5,8-trioxane (diethylene glycol dimethyl ether), diethyl ether, two Methyl ether, tetrahydrofuran, diphenyl ether, diisopropyl ether, and dimethyl ether of diethylene glycol; esters such as methyl acetate, dimethyl adipate, methyl benzoate, benzene Dimethyl formate and butyrolactone; guanamines such as dimethylacetamide, N-methyltetrahydropyrrolidone and dimethylformamide; steroids and terpenoids, such as dimethyl hydrazine, Di-isopropyl hydrazine, cyclobutyl hydrazine (tetrahydrothiophene-2,2-dioxide), 2-methylcyclobutyl hydrazine, diethyl hydrazine, tetrahydrothiophene 1,1-dioxide and 2-methyl 4-ethylcyclobutyl hydrazine; aromatic compounds, including halo-based variants of such compounds, such as benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, chlorobenzene, ortho - Dichlorobenzene, m-dichlorobenzene: alkanes, including halo-based variants of such compounds, such as hexane, heptane, 2,2,3-trimethylpentane, dichloromethane and carbon tetrachloride Nitriles such as benzonitrile and acetonitrile

Very suitable are aprotic solvents having a dielectric constant below 50 at 298.15 K and 1 x 10 ⁵ Nm ^-2 , more preferably in the range of 3 to 8. As used herein, the dielectric constant for a particular solvent is used in its normal sense to mean the ratio of the capacitance of the capacitor having the substance as a dielectric to the capacitance of the same capacitor having a vacuum for the dielectric. For the values of the dielectric constants of commonly used organic liquids, see the general reference books, for example, edited by David R. Lide et al., and published in 1995 by the CRC Press, Handbook of Chemistry and Physics, 76th Edition, and often cited, Regarding the temperature of about 20 ° C or 25 ° C. That is, about 293.15K or 298.15K, and atmospheric pressure, meaning about 1 x 10 ⁵ Nm ^-2 , or can be easily converted to the temperature and pressure using the cited conversion factor. If no literature data is available for a particular compound, the dielectric constant can be readily measured using established physico-chemical methods.

Measurements of the dielectric constant of the liquid can be readily performed by various sensors, such as immersion probes, flow-through probes, and cup-type probes, connected to various instruments, such as Brookhaven Instruments, Inc., available from Holtsville, NY (eg, Model BI-870) and Princeton, NJ's Scientifica (eg 850 and 870). To achieve consistency of comparison, all measurements for a particular filtration system are preferably performed at substantially the same sample temperature, such as with a water bath. In general, the measured dielectric constant of a substance will increase at lower temperatures and decrease at higher temperatures. The dielectric constant falling within any range herein can be determined in accordance with ASTM D924.

However, if you have doubts about which technique to use to measure the dielectric constant, you should use a Scientifica 870 dielectric constant meter with a range of 1-200 ε.

For example, the dielectric constant of toluene is 4.3 (at 294.2 K), the dielectric constant of diethyl ether is 4.3 (at 293.2 K), the dielectric constant of cyclobutadiene is 43.4 (at 303.2 K), valeric acid The dielectric constant of the ester is 5.0 (at 293.2 K), the dielectric constant of diphenyl ether is 3.7 (at 283.2 K), and the dielectric constant of dimethyl adipate is 6.8 (at 293.2 K). Tetrahydrofuran has a dielectric constant of 7.5 (at 295.2 K), methyl citrate has a dielectric constant of 3.9 (at 293.2 K), and methyl-tertiary-butyl ether has a dielectric constant of 4.34 (at 293 K). B), the dielectric constant of dioxane is 2.21 (at 298 K), the dielectric constant of toluene is 2.38 (at 298 K), and the dielectric constant of acetonitrile is 37.5 (at 298 K). These dielectric values are taken from the chemical and physical manuals and given the measured temperature. Preferably, the aprotic solvent is toluene ether.

In the presence of an alkanol, the aprotic solvent is produced by a reaction, and the ester carbonylation product of the ethylenically unsaturated compound, carbon monoxide and alkanol is an aprotic solvent.

This process can be carried out in an excess of aprotic solvent, meaning that the ratio of aprotic solvents to alkanols (v/v) is at least 1:1. This ratio range is preferably from 1:1 to 10:1, and more preferably from 1:1 to 5:1. This ratio (v/v) is optimally in the range of 1.5:1 to 3:1.

Although the foregoing, the reaction is preferably carried out in the absence of any externally added aprotic solvent, that is, in the absence of an aprotic solvent which is not produced by the reaction itself.

Alternatively, a protic cosolvent can be used. The protic cosolvent can include other carboxylic acids or alcohols. Suitable protic cosolvents include conventional protic solvents known to those skilled in the art, such as water, lower alcohols such as methanol, ethanol and isopropanol, and primary and secondary amines.

The presence of a protic solvent is also preferred during hydroxycarbonylation. The protic solvent can include a carboxylic acid or an alcohol. Mixtures of aprotic and protic solvents can also be employed.

By protonic cosolvent is meant any solvent with a hydrogen ion that can be administered, such as by attachment to oxygen such as in a hydroxyl group or nitrogen as in an amine group. By aprotic cosolvent is meant a type of solvent that neither supplies nor accepts protons.

Hydrogen can be added to the carbonylation reaction to improve the reaction rate. When used, an appropriate amount of hydrogen may be between 0.1 and 20% by volume/volume of carbon monoxide, more preferably 1 to 20% by volume/volume of carbon monoxide, more preferably 2 to 15% by volume/volume of carbon monoxide, most preferably 3- 10% by volume/volume of carbon monoxide.

The catalyst compound of the present invention can be used as a "heterogeneous" catalyst or a "homogeneous" catalyst, preferably a homogeneous catalyst.

By the term "homogeneous" catalyst, we mean a catalyst, meaning a compound of the invention, which is not supported, but only a reaction with a carbonylation reaction (for example, an ethylenically unsaturated compound). The hydroxy-containing compound and carbon monoxide are mixed or formed in situ, preferably in a suitable solvent as described herein.

By the term "heterogeneous" catalyst, we mean a catalyst, meaning a compound of the invention, which is carried on a support.

Thus, according to a further aspect, the present invention provides a process for the carbonylation of an ethylenically unsaturated compound, as defined herein, wherein the process is carried out as a catalyst comprising a support, preferably an insoluble support.

The support preferably comprises a polymer, such as a polyolefin, polystyrene, or a polystyrene copolymer, such as a divinylbenzene copolymer, or other suitable polymer or copolymer known to those skilled in the art; For example, functionalized vermiculite, polyoxyn oxide or polyoxyxene rubber; or other porous microparticle materials such as inorganic oxides and inorganic chlorides.

The support material is preferably a porous vermiculite having a surface area in the range of 10 to 700 m 2 /g, a total pore volume in the range of 0.1 to 4.0 cc / g, and an average in the range of 10 to 500 μm. Particle size. More preferably, the surface area is in the range of 50 to 500 m 2 /g, the pore volume is in the range of 0.5 to 2.5 cc / gram, and the average particle size is in the range of 20 to 200 μm. Most desirably, the surface area is in the range of 100 to 400 m 2 /g, the pore volume is in the range of 0.8 to 3.0 cc / gram, and the average particle size is in the range of 30 to 100 μm. Typical porous support materials have an average pore size of 10 to 1000 Within the scope. Preferably used with an average pore diameter of 50 to 500 The carrier material, and the most desirable is 75 to 350 . It may generally be particularly desirable to dehydrate the vermiculite for 3 to 24 hours at any temperature from 100 °C to 800 °C.

The support may suitably be a flexible or rigid support, and the insoluble support system is coated and/or impregnated with the compounds of the process of the invention by techniques known to those skilled in the art.

Alternatively, the compound of the method of the invention is immobilized to the surface of the insoluble support, optionally via a covalent bond, and the arrangement optionally includes a bifunctional spacer molecule to separate the compound from the insoluble support.

The compound of the present invention can be immobilized to an insoluble group by promoting the reaction of a functional group present in the ligand, such as a substituent of an aromatic structure, with a complementary reactive group present in or previously inserted into the support. The surface of the body. The combination of a reactive group of the support with a complementary substituent of a compound of the invention provides a heterogeneous catalyst wherein the compound of the invention and the support system are linked via a chain such as an ether, an ester, a guanamine, an amine, a urea, a ketone group. link.

The reaction conditions for linking the compound of the method of the present invention to the support are selected depending on the group of the ethylenically unsaturated compound and the support. For example, reagents such as carbodiimide, 1,1'-carbonyldiimidazole, and methods such as reductive amination using mixed anhydrides may be employed.

According to a further aspect, the invention provides the use of a method or ligand catalyst composition of any aspect of the invention, wherein the catalyst system is attached to a support.

In addition, the bidentate phosphine may be bonded to a suitable polymeric substrate via at least one bridging substituent, bridging group R, linking group A or linking group B, for example 1,2 bis (di-third-butyl) The phosphinylmethyl)-4-tri-butyl-benzene is preferably bonded to the polystyrene via 3, 5 or 6 cyclic carbons of the phenyl group to give a fixed heterogeneous catalyst.

The amount of ligand used can vary over a wide range. When an excess of the bidentate ligand is added, the bidentate ligand is preferably present in an amount such that the molar number of the bidentate ligand present is in the presence of the moieties of the Group 8, 9 or 10 metal. The number is from 1 to 50, for example from 1 to 15, and in particular from 1 to 10 moles per mole of metal. The ligand has a molar range for the Group 8, 9 or 10 metal: the molar range is preferably in the range of 1:1 to 20:1, and the optimum is in the range of 1:1 to 10:1 or even 1:1. To the range of 1.5:1. Conveniently, the possibility of applying such low molar ratios is advantageous as it avoids the use of excess ligands and thus minimizes the consumption of such generally expensive compounds. Suitably, the catalyst system of the present invention is prepared in a separate step prior to its use in the carbonylation reaction on the spot.

Conveniently, the process of the invention can be carried out by dissolving a Group 8, 9 or 10 metal complex as defined herein in a suitable solvent, such as one of the aforementioned alkanol or aprotic solvents (excellent) The solvent is the ester or acid product of a particular carbonylation reaction, for example, for the carbonylation of vinyl acetate to 2-ethyloxymethyl propionate or 3-ethyloxymethyl propionate, or for the carbonylation of ethylene. Methyl propionate).

Carbon monoxide can be used in the presence of other gases which are inert in the reaction. Examples of such gases include hydrogen, nitrogen, carbon dioxide, and noble gases such as argon.

The reaction product can be separated from other components by any suitable means. However, an advantage of the process of the present invention is the formation of significantly less by-products, thereby reducing the need for further purification after initial separation of the product. Another advantage is that other components containing the catalyst system can be recycled and/or reused in further reactions with the addition of minimal new catalyst.

A particular advantage is that metal anions are not present in the case of HCO ₃ ^- and CO ₃ ^{2- -} which are released as CO ₂ and water.

The carbonylation is preferably carried out at a temperature between -30 and 170 ° C, more preferably from -10 ° C to 160 ° C, most preferably from 20 ° C to 150 ° C. A particularly preferred temperature is selected from the group consisting of 40 ° C to 150 ° C. Advantageously, the carbonylation can be carried out at a suitable temperature, and it is particularly advantageous to be able to carry out the reaction at room temperature (20 ° C).

When the low temperature carbonylation is carried out, the carbonylation is preferably carried out between -30 ° C and 49 ° C, more preferably from -10 ° C to 45 ° C, still more preferably from 0 ° C to 45 ° C, most preferably 10 ° C. To 45 ° C. It is especially preferred in the range of 10 to 35 °C.

The carbonylation is preferably carried out at a CO partial pressure of between 0.80 x 10 ⁵ Nm ^{-2 and} 90 x 10 ⁵ Nm ^-2 , more preferably 1 x 10 ⁵ Nm ^-2 -65 x 10 ⁵ Nm ^-2 , most The best is 1-50 x 10 ⁵ Nm ^-2 . Particularly preferred is a partial pressure of CO of 5 to 45 x 10 ⁵ Nm ^-2 .

Lower pressure carbonylation is also preferred. When operating at a low pressure carbonylation, the carbonylation is preferably carried out at a partial pressure of CO of from 0.1 to 5 x 10 ⁵ Nm ^-2 , more preferably from 0.2 to 2 x 10 ⁵ Nm ^-2 , most preferably from 0.5 to 1.5 x 10 ⁵ Nm ^-2 .

There is no particular restriction on the duration of carbonylation, but carbonylation at a commercially acceptable ratio of time is clearly preferred. The carbonylation in the batch reaction can occur up to 48 hours, more typically up to 24 hours, and most typically up to 12 hours. Typically, the carbonylation system is at least 5 minutes, more typically at least 30 minutes, and most typically at least 1 hour. In a continuous reaction, such a time ratio is clearly uncorrelated, and the continuous reaction can continue as long as the TON is commercially acceptable before the catalyst needs to be replenished.

The catalyst system of the present invention is preferably constructed in the liquid phase which may be formed from one or more reactants or with a suitable solvent.

The stabilization of the compound with the use of a catalytic system can also be beneficial in improving the recovery of metals that have been lost from the catalyst system. When the catalyst system is utilized in a liquid reaction medium, such a stabilization compound can aid in the recovery of Group 8, 9 or 10 metals.

Accordingly, the catalyst system preferably comprises, in the liquid reaction medium, a polymeric dispersant which is dissolved in the liquid carrier, the polymeric dispersant being capable of causing the 8, 9, or 10 of the catalyst system in the liquid carrier. The colloidal suspension of the group metal or metal compound particles is stabilized.

The liquid reaction medium can be the solvent for the reaction or can contain one or more of the reactants or the reaction product itself. The reactants and reaction products in liquid form may be miscible with or dissolved in a solvent or liquid diluent.

The polymeric dispersant is soluble in the liquid reaction medium, but should not significantly increase the viscosity of the reaction medium in a manner that is detrimental to reaction kinetics or heat transfer. The solubility of the dispersant in the liquid medium under the reaction conditions of temperature and pressure should not be so great as to significantly impede the adsorption of the dispersant molecules on the metal particles.

The polymeric dispersant is capable of stabilizing a colloidal suspension of Group 8, 9 or 10 metal or metal compound particles in a liquid reaction medium such that the metal particles formed as a result of degradation of the catalyst are retained in suspension In liquid reaction media, and with liquids discharged from the reactor, for regeneration and, as appropriate, for the production of other amounts of catalyst. The metal particles are normally colloidal in size, for example in the range of 5-100 nm average particle size, although larger particles may be formed in some cases. a portion of the polymeric dispersant is adsorbed onto the surface of the metal particles, however, the remainder of the dispersant molecules are maintained at least partially solvated by the liquid reaction medium, and in this manner, the dispersed The Group 8, 9 or 10 metal particles are stabilized to prevent sedimentation on the walls of the reactor or in the dead space of the reactor, and to prevent the formation of agglomerates of metal particles which can be grown by collision of particles and finally Condensed. Some cohesiveness of the particles may occur even in the presence of a suitable dispersant, but when the type and concentration of the dispersant are optimized, the cohesion should be at a relatively low level and the cohesive polymer can only be loosely It is formed so that it can be broken, and the particles are redispersed by stirring.

The polymeric dispersant can include homopolymers or copolymers, including polymers such as graft copolymers and star polymers.

Preferably, the polymeric dispersant has sufficient acidic or basic functional groups to substantially stabilize the colloidal suspension of the Group 8, 9 or 10 metal or metal compound.

By substantially stabilized, it is meant that the precipitation of Group 8, 9 or 10 metals from the solution phase is substantially avoided.

Particularly preferred dispersants for this purpose include acidic or basic polymers, including carboxylic acids, sulfonic acids, amines and guanamines, such as polyacrylates, or heterocycles, especially nitrogen heterocycles, substituted A polyvinyl polymer such as polyvinyltetrahydropyrrolidone or a copolymer as described above.

Examples of such polymeric dispersants may be selected from the group consisting of polyvinyltetrahydropyrrolidone, polyacrylamide, polyacrylonitrile, polyethyleneimine, polyglycine, polyacrylic acid, polymethacrylic acid, poly(3- Hydroxybutyric acid), poly-L-leucine, poly-L-methionine, poly-L-proline, poly-L-serine, poly-L-tyrosine, poly(vinylbenzenesulfonic acid) Poly(vinylsulfonic acid), thiolated polyethyleneimine. Suitable thiolated polyethyleneimine systems are described in BASF Patent Publication No. EP1330309 A1 and US Pat. No. 6,723,882.

The polymeric dispersant preferably incorporates acidic or basic moiety groups, whether pendant or within the polymer backbone. Preferably, the acidic moiety-based solution having a dissociation constant of less than 6.0 (pK _a), more preferably less than 5.0 lines, the best lines below 4.5. Preferably, the basic moiety has a base dissociation constant (pK _b ) of less than 6.0, more preferably less than 5.0, and an optimum of less than 4.5, pK _a and pK _b are at 25 ° C in a dilute aqueous solution. Metric.

Suitable polymeric dispersants, in addition to being soluble in the reaction medium under the reaction conditions, contain at least one acidic or basic moiety, either in the polymer backbone or as a pendant group. It has been found that polymers incorporating acid and guanamine moiety, such as polyvinyltetrahydropyrrolidone (PVP), and polyacrylates, such as polyacrylic acid (PAA), are particularly suitable. The molecular weight of the polymer suitable for use in the present invention will depend on the nature of the reaction medium and the solubility of the polymer therein. We have found that the average molecular weight is less than 100,000 under normal conditions. The average molecular weight is preferably in the range of 1,000 to 200,000, more preferably 5,000 to 100,000, most preferably 10,000 to 40,000. For example, when PVP is used, Mw is preferably in the range of 10,000 to 80,000, more preferably 20,000. 60,000, and in the case of PAA, it is in the spectrum of 1,000-10,000.

The effective concentration of the dispersant in the reaction medium should be determined for each reaction/catalyst system to be used.

The dispersed Group 8, 9 or 10 metals can be recovered from the stream removed from the reactor, such as by filtration, and then either disposed of, or disposed of for reuse as a catalyst or other application. In a continuous process, the liquid stream can be circulated through an external heat exchanger, and in this case it is expedient to position the palladium particles with the filter in such a recycle unit.

Polymer: metal mass ratio, expressed in grams per gram, preferably between 1:1 and 1000:1, more preferably between 1:1 and 400:1, optimally between 1:1 and 200 Between:1. Polymer: Metal mass ratio, expressed in grams per gram, preferably up to 1000, more preferably up to 400, most preferably up to 200.

It should be understood that any feature presented in the first aspect of the invention may be considered to be a preferred feature of the second, third, fourth, fifth or other aspects of the invention, and vice versa.

The invention extends not only to novel complexes, but also to novel catalyst systems incorporating such complexes.

The metal complex according to the present invention and the production of its catalytic activity are described in the following non-limiting examples, and reference is made to Figure 1.

Example 1

The tetraamine di(hydrogen carbonate) palladium was suspended in methanol with 1 molar equivalent of 1,2-bis(di-tert-butylphosphinomethyl)benzene under reflux for 6 hours. Alkaline gas (salt is ammonia) is released during the reaction. The product was filtered off at room temperature and dried. This product was recrystallized from hot methanol and the crystals were characterized by single crystal X-ray diffraction. The product was identified as Pd(1,2-bis(di-tert-butylphosphinomethyl)benzene)(CO ₃ ).2CH ₃ OH (see Figure 1). The dried product contained 18.82% Pd by standard wet chemical analysis, which was consistent with the compound as Pd (1,2-bis(di-t-butylphosphinomethyl)benzene) (CO ₃ ). Further support confirmation by infrared spectroscopy was also obtained.

Example 2

The tetramine di(hydrogen carbonate) palladium and 1 molar equivalent of 1,2-bis(di-tert-butylphosphinomethyl)dicyclopentadienyl iron were suspended in methanol under reflux for 6 hours. Alkaline gas (salt is ammonia) is released during the reaction. The product was filtered off at room temperature and dried. The product contained 15.95% Pd by standard wet chemical analysis and was identified as Pd(1,2-bis(di-t-butylphosphinomethyl)dicyclopentadienyl iron) (CO ₃ ) with the compound. Consistent. Further support confirmation by infrared spectroscopy was also obtained.

Example 3

The tetraammine bis(hydrogen carbonate) palladium and 1 molar equivalent of 1,2-bis(di-3,5,dimethyl gold steel alkylphosphinomethyl)dicyclopentadienyl iron are suspended under reflux 6 hours in methanol. Alkaline gas (salt is ammonia) is released during the reaction. The product was filtered off at room temperature and dried. By standard wet chemical analysis, the product contained 9.60% Pd, which was identified as Pd (1,2-bis((di-3,5,dimethyl gold alkyl)phosphinomethyl)dicyclopenta The diene iron) (CO ₃ ) is consistent. Further support confirmation by infrared spectroscopy was also obtained.

Example 4

The tetraammine bis(hydrogen carbonate) palladium is refluxed with 1 molar equivalent of cis-1,2-bis(di-t-butyl-butylphosphinomethyl)-4,5-dimethylcyclohexane. The suspension was suspended in methanol for 6 hours. Alkaline gas (salt is ammonia) is released during the reaction. The product was filtered off at room temperature and dried. The product contained 17.72% Pd by standard wet chemical analysis and was identified as Pd (cis-1,2-bis(di-tertiary-butylphosphinomethyl) 4,5-dimethyl Cyclohexane (CO ₃ ) was consistent. Further support confirmation by infrared spectroscopy was also obtained.

Catalyst test Test complex 1

The solution used for the catalyst test was prepared using standard Schlenk pipeline technology as described below. 10.58 mg (L-L) PdCO ₃ (1.45*10 ^-5 mol) complex (L-L) = 1,2-bis(di-tertiary-butylphosphine) in a nitrogen scrubbing glove box The methylidene dicyclopentadienyl iron was replaced with 5 equivalents of the phosphine ligand (L-L) (7.25*10 ^-5 mol) in a 500 ml round bottom flask. The flask was then transferred to the Schlenk line. Next, the palladium complex and the excess ligand were dissolved in 125 ml of degassed methyl propionate followed by 175 ml of degassed methyl propionate/methanol mixture (50% by weight methanol, 50% by weight). Methyl propionate). The addition of 420 microliters of methanesulfonic acid (MSA) was compared to the comparison of tests 1 and 2 below to complete the preparation of the catalyst solution in a much shorter period of time. In addition, the addition of acid releases carbon dioxide gas and water, which does not contaminate the reaction system. The final composition of the solution was approximately 70% by weight methyl propionate, 30% by weight methanol.

The catalytic solution was added to a pre-exhausted autoclave and heated to 100 °C. Then, the autoclave was pressurized at 8 bar ethylene higher than the vapor pressure to obtain a total pressure of 10.2 bar at 100 °C. Next, the autoclave was pressurized to 12.2 bar by adding CO:ethylene (1:1 gas) charged from a 10 liter storage tank. The regulating valve system ensures that the pressure of the autoclave is constant injection through a gas from a 10 liter reservoir throughout the reaction and is maintained at 12.2 bar. The pressure in the reservoir and the reactor temperature were recorded during the entire 3 hour reaction period.

The number of moles produced at any point in any of the reactions is calculated by assuming assuming that the ideal gas behavior is 100% selective for methyl propionate, which allows for a reduction in the pressure from the reservoir, which allows the reaction TON to be obtained. rate. The results are shown in Table 1.

Test complex 2

The solution used for the catalyst test was made according to the example ligand 1, using standard Schlenk pipeline technology. In a nitrogen scrub glove box, 16.73 mg (L-L) PdCO ₃ (1.45*10 ^-5 mol) complex (L-L) = 1,2-bis (di-1-(3,5) - Dimethyl fund steel alkyl) phosphinomethyl) dicyclopentadienyl iron with 5 equivalents of phosphine ligand (L-L) (7.25 * 10 ^-5 mol) is reset to 500 ml round bottom flask in. The flask was then transferred to the Schlenk line. Next, the palladium complex and the excess ligand were dissolved in 125 ml of degassed methyl propionate followed by 175 ml of degassed methyl propionate/methanol mixture (50% by weight methanol, 50% by weight). Methyl propionate). The addition of methanesulfonic acid (MSA) 420 microliters compared to the comparison of tests 1 and 2 below completes the preparation of the catalyst solution over a much shorter period of time. In addition, the addition of acid releases carbon dioxide gas and water, which does not contaminate the reaction system. The final composition of the solution was approximately 70% by weight methyl propionate, 30% by weight methanol.

The catalytic solution was added to a pre-exhausted autoclave and heated to 100 °C. Then, the autoclave was pressurized at 8 bar ethylene higher than the vapor pressure to obtain a total pressure of 10.2 bar at 100 °C. Next, the autoclave was pressurized to 12.2 bar by adding CO:ethylene (1:1 gas) charged from a 10 liter storage tank. The regulating valve system ensures that the pressure of the autoclave is constant injection through a gas from a 10 liter reservoir throughout the reaction and is maintained at 12.2 bar. The pressure in the reservoir and the reactor temperature were recorded during the entire 3 hour reaction period.

The number of moles produced at any point in any of the reactions is calculated by assuming assuming that the ideal gas behavior is 100% selective for methyl propionate, which allows for a reduction in the pressure from the reservoir, which allows the reaction TON to be obtained. rate. The results are shown in Table 1.

Comparison of Pd(dba) test complex 1

Solutions for catalyst testing were made using standard Schlenk piping technology. In a nitrogen scrub glove box, 7.8 mg of Pd ₂ dba ₃ (1.45*10 ^-5 mol) and 6 equivalents of phosphine ligand 1 (L-L) = 1,2-double (di-third - The butylphosphinomethyl)dicyclopentadienyl iron (8.7*10 ^-5 mol) was placed in a 500 ml round bottom flask. The flask was then transferred to the Schlenk line. Next, the ligand and palladium were dissolved in 125 ml of degassed methyl propionate. To aid in the mismatch, the palladium and ligand were first dissolved in methyl propionate and stirred for 45 minutes, then other solvents were added to the solution. This allows the formation of a neutral triangular planar Pd(0) complex [Pd (ligand) (dba)].

After the mismatch, 175 ml of a methyl propionate/methanol mixture (50% by weight of methanol, 50% by weight of methyl propionate) was degassed and added to the flask. Methanesulfonic acid (MSA), 420 microliters of addition, is the completion of the preparation of the catalyst solution. However, dba still exists in the system. The final composition of the solution was approximately 70% by weight methyl propionate, 30% by weight methanol.

The catalytic solution was added to a pre-exhausted autoclave and heated to 100 °C. Then, the autoclave was pressurized at 8 bar ethylene higher than the vapor pressure to obtain a total pressure of 10.2 bar at 100 °C. Next, the autoclave was pressurized to 12.2 bar by adding CO:ethylene (1:1 gas) charged from a 10 liter storage tank. The regulating valve system ensures that the pressure of the autoclave is constant injection through a gas from a 10 liter reservoir throughout the reaction and is maintained at 12.2 bar. The pressure in the reservoir and the reactor temperature were recorded during the entire 3 hour reaction period.

The number of moles produced at any point in any of the reactions is calculated by assuming assuming that the ideal gas behavior is 100% selective for methyl propionate, which allows for a reduction in the pressure from the reservoir, which allows the reaction TON to be obtained. rate. The results are shown in Table 1.

Comparison test using Pd(dba) 2

Solutions for catalyst testing were made using standard Schlenk piping technology. In a nitrogen scrubbing glove box, 7.8 mg of Pd ₂ dba ₃ (1.45*10 ^-5 mol) and 6 equivalents of phosphine ligand 2 (L-L) = 1,2-bis (di-1-() The 3,5-dimethyl fund steel alkyl)phosphinylmethyl)dicyclopentadienyl iron (8.7*10 ^-5 mol) was reset in a 500 ml round bottom flask. The flask was then transferred to the Schlenk line. Next, the ligand and palladium were dissolved in 125 ml of degassed methyl propionate. To aid in the mismatch, the palladium and ligand were first dissolved in methyl propionate and stirred for 45 minutes, then other solvents were added to the solution. This allows the formation of a neutral triangular planar Pd(0) complex [Pd (ligand) (dba)].

After the mismatch, 175 ml of a methyl propionate/methanol mixture (50% by weight of methanol, 50% by weight of methyl propionate) was degassed and added to the flask. Methanesulfonic acid (MSA), 420 microliters of addition, is the completion of the preparation of the catalyst solution. However, dba still exists in the system. The final composition of the solution was approximately 70% by weight methyl propionate, 30% by weight methanol.

The catalytic solution was added to a pre-exhausted autoclave and heated to 100 °C. Then, the autoclave was pressurized at 8 bar ethylene higher than the vapor pressure to obtain a total pressure of 10.2 bar at 100 °C. Next, the autoclave was pressurized to 12.2 bar by adding CO:ethylene (1:1 gas) charged from a 10 liter storage tank. The regulating valve system ensures that the pressure of the autoclave is constant injection through a gas from a 10 liter reservoir throughout the reaction and is maintained at 12.2 bar. The pressure in the reservoir and the reactor temperature were recorded during the entire 3 hour reaction period.

The number of moles produced at any point in any of the reactions is calculated by assuming assuming that the ideal gas behavior is 100% selective for methyl propionate, which allows for a reduction in the pressure from the reservoir, which allows the reaction TON to be obtained. rate. The results are shown in Table 1.

In the above batch example, the coordination system was added in a ratio of 6 equivalents to the metal, and then the acid was added in a ratio of 450 equivalents to the metal. With such a large excess of acid, there is no need to balance the system and the metal will readily be oxidized in both systems.

However, in a continuous process, such large excesses of acid are not maintained and will cause corrosion to the reactor and piping. Likewise, ligands are expensive commodities, and a large excess of such ligands will increase the expense of continuous industrial processes. Using a much lower level of ligand, the balance of the complex will take longer for a dba-based system, however the system of the invention will achieve rapid equilibrium. Similarly, the use of less acid in a continuous system means that the metal is oxidized from Pd(0) to Pd(II) to a longer oxidation period. In the system of the present invention, the metal is in an active oxidized state, so that no equilibrium is required. Thus, the second stage of catalyst preparation is also rapidly accelerated using the metal complex of the present invention.

The reader's attention is directed to all papers and documents presented at the same time as or prior to this patent specification of the present application, and is open to the public for review along with this patent specification, and the contents of all such papers and documents are And for reference in this article.

All the features disclosed in this patent specification (including any claims, abstracts and drawings attached to the accompanying claims), and/or all steps of any method or process so disclosed may be combined in any combination, but at least Some such features and/or steps are excluded from combinations of mutual exclusion.

The features disclosed in this patent specification, including any claims, abstracts, and drawings, which are incorporated in the specification, may be substituted for the same, equivalent, or similar features unless otherwise specifically stated. Accordingly, unless expressly stated otherwise, the features disclosed are only one example of the equivalent or similar features of the generic series.

The invention is not limited to the details of the specific embodiments described above. The present invention extends to any novel or any novel combination of the features disclosed in this patent specification (including any claims, abstracts and drawings attached hereto), or to any of the methods or processes disclosed herein. Any novelty or any novel combination.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a molecular diagram of a metal complex according to the present invention.

Claims (16)

A metal complex ML _n X _m , wherein M is a metal of Group 8, 9 or 10, and L is a formula (I), (II), (III), (IV) or (V) as shown below A bidentate phosphine ligand, X is HCO ₃ ^- or CO ₃ ^2- , n is equal to or less than the number of metal coordination numbers, m is 1 or 2, and is equal to the oxidation state of the metal: Wherein: Ar is a bridging group comprising an optionally substituted aryl moiety, the phosphorus atom is bonded to the group at adjacent carbon atoms; and A and B each independently represent a lower alkylene group. ; K, D, E and Z are substituents of the aryl moiety (Ar), and each independently represents hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , C(S)R ²⁵ R ²⁶ , SR ²⁷ , C(O SR ²⁷ or -JQ ³ (CR ¹³ (R ¹⁴ )(R ¹⁵ )CR ¹⁶ (R ¹⁷ )(R ¹⁸ ), wherein J represents a lower alkylene group; or two selected from K, Z, D and E Adjacent groups, together with the carbon atoms of the aryl ring to which they are attached, form another phenyl ring which is optionally substituted with one or more substituents selected from the group consisting of hydrogen, lower alkyl, halogen Base, cyano, nitro, OR ¹⁹ , OC(O)R ²⁰ , C(O)R ²¹ , C(O)OR ²² , NR ²³ R ²⁴ , C(O)NR ²⁵ R ²⁶ , C(S) R ²⁵ R ²⁶ , SR ²⁷ or C(O)SR ²⁷ ; R ¹³ to R ¹⁸ each independently represent hydrogen, lower alkyl, aryl or Het, preferably each independently represents lower alkyl, aryl or Het. ; R ¹⁹ to R ²⁷ each independently table Hydrogen, lower alkyl, aryl or Het; R ¹ to R ¹² each independently represents hydrogen, lower alkyl, aryl, or Het, preferably each independently represent lower alkyl-based, aryl or Het; Q ¹ , Q ² and Q ³ (when present) each independently represent phosphorus, arsenic or antimony, and in the latter case, the reference to the above phosphine or phosphorus is modified accordingly; Wherein: A ₁ and A ₂ , and A ₃ , A ₄ and A ₅ (when present) each independently represent a lower carbene alkyl group; K ¹ is selected from the group consisting of hydrogen, lower alkyl, aryl, Het, Halo, cyano, nitro, -OR ¹⁹ , -OC(O)R ²⁰ , -C(O)R ²¹ , -C(O)OR ²² , -N(R ²³ )R ²⁴ , -C(O N(R ²⁵ )R ²⁶ , -C(S)(R ²⁷ )R ²⁸ , -SR ²⁹ , -C(O)SR ³⁰ , -CF ₃ or -A ₃ -Q ³ (X ⁵ )X ⁶ ; D ¹ is selected from the group consisting of hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, -OR ¹⁹ , -OC(O)R ²⁰ , -C(O)R ²¹ , -C( O) OR ²² , -N(R ²³ )R ²⁴ , -C(O)N(R ²⁵ )R ²⁶ , -C(S)(R ²⁷ )R ²⁸ , -SR ²⁹ , -C(O)SR ³⁰ , -CF ₃ or -A ₄ -Q ⁴ (X ⁷ )X ⁸ ; E ¹ is selected from the group consisting of hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, -OR ¹⁹ , - OC(O)R ²⁰ , -C(O)R ²¹ , -C(O)OR ²² , -N(R ²³ )R ²⁴ , -C(O)N(R ²⁵ )R ²⁶ , -C(S) (R ²⁷ )R ²⁸ , -SR ²⁹ , -C(O)SR ³⁰ , -CF ₃ or -A ₅ -Q ⁵ (X ⁹ )X ¹⁰ ; or both D ¹ and E ¹ and their together with the carbon atoms of the cyclopentadienyl ring of an optionally substituted phenyl ring: X ¹ represents ^{CR 1 (R 2) (R} 3), two or adamantyl alkoxy magic , X ² represents a ^{CR 4 (R 5) (R} 6), two adamantyl or adamantyl, or X ^{1 2} optionally together form with their X ² and Q are connected via the three substituents of the 2-phospha ring and [3.3.1.1 {3,7}] decyl group or a derivative thereof, or X ^{1 2} together form a ring system of formula IIIa with X ² and their connected the Q X ³ represents CR ⁷ (R ⁸ )(R ⁹ ), diamantyl or gold alkyl, and X ⁴ represents CR ¹⁰ (R ¹¹ )(R ¹² ), diamantyl or gold alkyl, or X ³ together with X ⁴ and the Q ¹ to which they are attached form an optionally substituted 2-phosphorus tris[3.3.1.1{3,7}] fluorenyl group or a derivative thereof, or X ³ and X ⁴ and Waiting for the connected Q ¹ to form the ring system of formula IIIb X ⁵ represents CR ¹³ (R ¹⁴ )(R ¹⁵ ), diamantyl or gold steel alkyl, and X ⁶ represents CR ¹⁶ (R ¹⁷ )(R ¹⁸ ), diamantyl or gold alkyl, or X ^5, together with X ⁶ and the Q ³ to which they are attached, form an optionally substituted 2-phosphoric tricyclic [3.3.1.1{3,7}] fluorenyl group or a derivative thereof, or X ⁵ and X ⁶ and And the connected Q ³ together form a ring system of the formula IIIc X ⁷ represents CR ³¹ (R ³² )(R ³³ ), diamantyl or gold steel alkyl, and X ⁸ represents CR ³⁴ (R ³⁵ ) (R ³⁶ ), diamantyl or gold alkyl, or X ⁷ together with X ⁸ and the Q ⁴ to which they are attached form an optionally substituted 2-phosphoric tricyclic [3.3.1.1{3,7}] fluorenyl group or a derivative thereof, or X ⁷ and X ⁸ and Waiting for the connected Q ⁴ to form the ring system of formula IIId X ⁹ represents CR ³⁷ (R ³⁸ )(R ³⁹ ), diamantyl or gold alkyl, and X ¹⁰ represents CR ⁴⁰ (R ⁴¹ )(R ⁴² ), diamantyl or gold alkyl, or X ⁹ together with X ¹⁰ and the Q ⁵ to which they are attached form an optionally substituted 2-phosphoric tricyclic [3.3.1.1.{3,7}] fluorenyl group or a derivative thereof, or X ⁹ and X ¹⁰ and The Q ^5s connected to them form a ring system of the formula IIIe And in still further embodiments, Q ¹ and Q ² and Q ³ , Q ⁴ and Q ⁵ (when present) each independently represent phosphorus, arsenic or antimony; M represents a Group VIB or VIIIB metal or a metal cation thereof ; L ₁ represents optionally substituted cyclopentadienyl, indenyl or aryl; L ₂ represents one or more ligands, each of which is independently selected from hydrogen, lower alkyl, alkylaryl , halo, CO, P(R ⁴³ )(R ⁴⁴ )R ⁴⁵ or N(R ⁴⁶ )(R ⁴⁷ )R ⁴⁸ ; R ¹ to R ¹⁸ and R ³¹ to R ⁴² , when present, each independently represent hydrogen , lower alkyl, aryl, halo or Het; R ¹⁹ to R ³⁰ and R ⁴³ to R ⁴⁸ , when present, each independently represent hydrogen, lower alkyl, aryl or Het; R ⁴⁹ , R ⁵⁴ And R ⁵⁵ , when present, each independently represent hydrogen, lower alkyl or aryl; R ⁵⁰ to R ⁵³ , when present, each independently represent hydrogen, lower alkyl, aryl or Het; Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ , when present, each independently represents oxygen, sulfur or NR ⁵⁵ ; n = 0 or 1; and m = 0 to 5; the condition is that when n = 1, then m Is equal to 0, and when n is equal to 0, then m is not equal to 0; general formula (III) X ¹ (X ² )-Q ² -ARBQ ¹ -X ³ (X ⁴ ) where: A And B are as defined below with respect to formula (IV); R represents optionally substituted cycloalkyl moiety, and Q ¹ and Q ² atomic groups are bonded to the adjacent cyclic carbon atom which may be employed a group; the groups X ¹ , X ² , X ³ and X ⁴ are as defined below with respect to formula (IV); both Q ¹ and Q ² are as defined below with respect to formula (IV); X1(X2)-Q ² -ARBQ ¹ -X3(X4) wherein: A and B each independently represent a lower alkylidene group; R represents a cyclic hydrocarbyl structure having at least one non-aromatic ring, Q ¹ and Q ² atoms Attaching to the ring at an adjacent ring atom of the at least one ring, and the ring system is substituted with at least one substituent on at least one other non-adjacent ring atom of the at least one ring; Adjacent ring atoms of adjacent ring atoms are not substituted to pass adjacent ring atoms through another adjacent ring atom to the adjacent ring atoms, or via adjacent to the other adjacent atom but at least An atom outside the ring forms another 3-8 atomic ring structure; the groups X1, X2, X3 and X4 independently represent a monovalent group, up to 30 atoms, with at least one tertiary An atom, or X1 and X2 and/or X3 and X4 together form a divalent group of up to 40 atoms, having at least two tertiary carbon atoms, wherein each of the monovalent or divalent groups is via the at least one or two The tertiary carbon atoms are individually bonded to the appropriate atom Q ¹ or Q ² ; and Q ¹ and Q ² each independently represent phosphorus, arsenic or antimony; Wherein: A and B are as defined in formula (IV); R represents a hydrocarbyl aromatic structure having at least one aromatic ring, and Q ¹ and Q ² are each bonded to the ring via an individual linking group, at least one The aromatic ring may be on an adjacent ring atom, and the ring system is substituted on one or more of the other aromatic ring atoms by one or more substituents Y ^x ; wherein the substitution in the aromatic structure The base Y ^x has a total number of atoms other than hydrogen ^{X = 1 - n} Σ tY ^x such that ^{X = 1 - n} ΣtY ^x ≧ 4, where n is the total number of substituents Y ^x and tY ^{x is} represented on the specific substituent Y ^x The total number of atoms other than hydrogen; the groups X ¹ , X ² , X ³ and X ⁴ are as defined in formula (IV); and both Q ¹ and Q ² are as defined in formula (IV). The metal complex of claim 1, wherein both Q ¹ and Q ² represent phosphorus. The metal complex of claim 1, wherein Q ^{3 is} present and Q ¹ , Q ² and Q ³ each represent phosphorus. The metal complex of claim 1, wherein the phosphine is selected from the group consisting of 1,2-bis-(di-t-butylphosphinomethyl)benzene, 1,2-bis-(di-third- Butylphosphinomethyl)benzene, 1,2-bis-(di-tertiary-butylphosphinomethyl)1,2-bis(di-gold-steel alkylphosphinomethyl)benzene, 1,2-bis(di-3,5-dimethyl fund steel alkylphosphinomethyl)benzene, 1,2-double ( Bi-5-third-buty fund steel alkylphosphinomethyl)benzene, 1,2-bis(1-gold steel alkyl-tert-butyl-phosphinomethyl)benzene, 1-(di gold steel Alkylphosphinomethyl)-2-(di-tertiary-butylphosphinomethyl)benzene, 1-(di-tertiary-butylphosphinomethyl)-2-(di-adamantylphosphine) Methyl)benzene, 1-(di-t-butylphosphinomethyl)-2-(phosphorus-gold-steel alkyl-P-methyl)benzene, 1-(di-gold-steel alkylphosphino) Base)-2-(phosphorus-gold steel alkyl-P-methyl)benzene, 1-(third-butane fund steel alkylphosphinomethyl)-2-(di-gold steel alkylphosphinomethyl Benzene and 1-[(P-(2,2,6,6,-tetra-methylphosphino-4-one)phosphinomethyl)]-2-(phosphorus-gold steel alkyl-P- Benzene, wherein "phosphorus-gold steel alkyl" is selected from 2-phosphorus-1,3,5,7-tetramethyl-6,9,10-trioxy gold steel alkyl, 2-phosphorus-1 , 3,5-trimethyl-6,9,10 trioxy gold steel alkyl, 2-phosphorus-1,3,5,7-tetrakis(trifluoromethyl)-6,9,10-trioxy gold Steel alkyl or 2-phosphorus-1,3,5-tris(trifluoromethyl)-6,9,10-trioxy gold steel alkyl; 1,2-bis-(dimethylaminomethyl) Cyclopentadienyl iron, 1,2-bis-(di-t-butylphosphino) Dicyclopentadienyl iron, 1-hydroxymethyl-2-dimethylaminomethyldicyclopentadienyl iron, 1,2-bis-(di-t-butylphosphinomethyl)dicyclopentane Diene iron, 1-hydroxymethyl-2,3-bis-(dimethylaminomethyl)dicyclopentadienyl iron, 1,2,3-para-(di-tert-butylphosphinomethyl) Iron dicyclopentadiene, iron 1,2-bis-(dicyclohexylphosphinomethyl)dicyclopentadiene, 1,2-bis-(di-isobutylphosphinomethyl)dicyclopentan Iron diene, 1,2-bis-(dicyclopentylphosphinomethyl)dicyclopentadienyl iron, 1,2-bis-(diethylphosphinomethyl)dicyclopentadienyl iron, 1 , 2-bis(di-isopropylphosphinomethyl)dicyclopentadienyl iron, 1,2-bis-(dimethylphosphinomethyl)dicyclopentadienyl iron, 1,2-double- (bis-(1,3,5,7-tetramethyl-6,9,10-trioxo-2-phosphorus-gold steel alkylmethyl)) dicyclopentadienyl iron, 1,2-double- (dimethylaminomethyl)dicyclopentadienyl iron-diiodinated methane, 1,2-bis(dihydroxymethylphosphine) Methyl)dicyclopentadienyl iron, 1,2-bis(diphosphinomethyl)dicyclopentadienyl iron, 1,2-bis-α,α-(P-(2,2,6, 6,-tetramethylphosphino-4-one)) dimethyl dicyclopentadienyl iron and 1,2-bis-(di-1,3,5,7-tetramethyl-6,9,10 -trioxo-2-phosphorus-gold steel alkylmethyl))benzene; cis-1,2-bis(di-t-butyl-butylphosphinomethyl)-4,5-dimethylcyclohexane ;cis-1,2-bis(di-tertiary-butylphosphinomethyl)-5-methylcyclopentane; cis-1,2-bis(2-phosphinomethyl-1,3 ,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4,5-dimethylcyclohexane; cis-1,2-bis(2-phosphinomethyl -1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl) 5-methylcyclopentane; cis-1,2-bis(di-gold steel alkyl Phosphylmethyl)-4,5-dimethylcyclohexane; cis-1,2-bis(di-gold steel alkylphosphinomethyl)-5-methylcyclopentane; cis-1- (P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl)-4,5-dimethylcyclohexane; cis- 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butyl-butylphosphinomethyl)-5-methylcyclopentane; cis-1 -(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di- Tri-butylphosphinomethyl)-4,5-dimethylcyclohexane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9, 10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-5-methylcyclopentane; cis-1-(2-phosphinomethyl-1, 3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-5-methylcyclohexane; cis- 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl) -5-methylcyclopentane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2 -(二金钢alkylphosphinomethyl)cyclobutane; cis-1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4 ,5-dimethylcyclohexane; cis-1-(di-tertiary-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-5-methylcyclopentane ;cis-1,2-bis(2-phospho-1,3,5-trimethyl-6,9,10-trioxatricyclo -{3. 3. 1. 1[3. 7]} mercapto)-4,5-dimethylcyclohexane; cis-1,2-bis(2-phosphorus-1,3,5-trimethyl-6,9,10-trioxane环和-{3. 3. 1. 1[3. 7]} mercapto)-5-methylcyclopentane; cis-1-(2-phospho-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)-4,5-dimethylcyclohexane; cis-1-(2-phosphorus-1,3,5- Trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-tertiary-butylphosphinomethyl)-5-methylcyclopentane; cis-1-(2-phospho-1,3,5-trimethyl -6,9,10-trioxytricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-dimethylcyclohexane; cis-1-(2-phosphorus-1,3,5-trimethyl Base-6,9,10-trioxytricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-5-methylcyclopentane; cis-1,2-bis-perfluoro(2-phosphorus-1,3,5 , 7-tetramethyl-6,9,10-trioxane and {3. 3. 1. 1[3. 7]}-mercapto)-4,5-dimethylcyclohexane; cis-1,2-bis-perfluoro(2-phosphorus-1,3,5,7-tetramethyl-6,9 , 10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-5-methylcyclopentane; cis-1,2-bis-(2-phosphino-1,3,5,7-tetra(trifluoro-methyl)-6,9, 10-trioxane ring and {3. 3. 1. 1[3. 7]} mercapto)-4,5-dimethylcyclohexane; cis-1,2-bis-(2-phospho-1,3,5,7-tetra(trifluoro-methyl)-6 , 9,10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-5-methylcyclopentane; cis-1,2-bis(di-tertiary-butylphosphinomethyl)cyclohexane; cis-1,2-di(di) -T-butylphosphinomethyl)cyclopentane; cis-1,2-bis(di-tertiary-butylphosphinomethyl)cyclobutane; cis-1,2-dual (2 -phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold steel alkyl)cyclohexane; cis-1,2-bis(2-phosphino) Base-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)cyclopentane; cis-1,2-bis(2-phosphinomethyl-1, 3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)cyclobutane; cis-1,2-bis(di-gold steel alkylphosphinomethyl)cyclohexane Alkane; cis-1,2-bis(di-gold steel alkylphosphinomethyl)cyclopentane; cis-1,2-bis(di-gold steel alkylphosphinomethyl)cyclobutane; Cis-1-(P,P-gold steel alkyl Tri-butyl-phosphinomethyl)-2-(di-t-butylphosphinomethyl)cyclohexane; cis-1-(P,P-gold steel alkyl-tert-butyl- Phosphylmethyl)-2-(di-t-butylphosphinomethyl)cyclopentane; cis-1-(P,P-gold steel alkyl-tert-butyl-phosphinomethyl) -2-(di-t-butylphosphinomethyl)cyclobutane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10 -trioxo-gold steel alkyl)-2-(di-t-butylphosphinomethyl)cyclohexane; cis-1-(2-phosphinomethyl-1,3,5,7- Tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl)cyclopentane; cis-1-(2-phosphinomethyl -1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl)cyclobutane; cis- 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl) Cyclohexane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold steel Alkylphosphinomethyl)cyclopentane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl) -2-(di-gold-steel alkylphosphinomethyl)cyclobutane; cis-1-(di-tertiary-butylphosphinomethyl)-2 -(二金钢alkylphosphinomethyl)cyclohexane; cis-1-(di-tertiary-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)cyclopentane Alkane; cis-1-(di-tertiary-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)cyclobutane; cis-1,2-bis(2-phosphorus -1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto) cyclohexane; cis-1,2-bis(2-phosphino-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto) cyclopentane; cis-1,2-bis(2-phospho-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto) cyclobutane; cis-1-(2-phospho-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-tertiary-butylphosphinomethyl)cyclohexane; cis-1-(2-phospho-1,3,5-trimethyl-6,9, 10-trioxane--3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)cyclopentane; cis-1-(2-phospho-1,3,5-trimethyl-6,9, 10-trioxane -{3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)cyclobutane; cis-1-(2-phospho-1,3,5-trimethyl-6,9, 10-trioxane--3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)cyclohexane; cis-1-(2-phospho-1,3,5-trimethyl-6,9,10- Trioxane and -{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)cyclopentane; cis-1-(2-phospho-1,3,5-trimethyl-6,9,10- Trioxane and -{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)cyclobutane; cis-1,2-bis-perfluoro(2-phosphorus-1,3,5,7-tetramethyl) Base-6,9,10-trioxane and {3. 3. 1. 1[3. 7]}-mercapto)cyclohexane; cis-1,2-bis-perfluoro(2-phospho-1,3,5,7-tetramethyl-6,9,10-trioxane {3. 3. 1. 1[3. 7]} mercapto) cyclopentane; cis-1,2-bis-perfluoro(2-phosphorus-1,3,5,7-tetramethyl-6,9,10-trioxane) 3. 3. 1. 1[3. 7]} mercapto) cyclobutane; cis-1,2-bis-(2-phospho-1,3,5,7-tetra(trifluoro-methyl)-6,9,10-trioxane Ring and {3. 3. 1. 1[3. 7]} mercapto) cyclohexane; cis-1,2-bis-(2-phospho-1,3,5,7-tetra(trifluoro-methyl)-6,9,10-trioxane Ring and {3. 3. 1. 1[3. 7]} mercapto) cyclopentane; cis-1,2-bis-(2-phospho-1,3,5,7-tetra(trifluoro-methyl)-6,9,10-trioxane Ring and {3. 3. 1. 1[3. 7]} fluorenyl) cyclobutane; (2-extroversion, 3-external)-bicyclic and [2. 2. 1] heptane-2,3-bis(di-tertiary-butylphosphinomethyl); (2-introverted, 3-intro)-bicyclic [2. 2. 1] heptane-2,3-bis(di-tertiary-butylphosphinomethyl); 1,2-bis(di-tertiary-butylphosphinomethyl)-4,5-diphenyl Benzene; 1,2-bis(di-t-butylphosphinomethyl)-4-phenylbenzene; 1,2-bis(di-tertiary-butylphosphinomethyl)-4,5- Bis-(trimethyldecyl)benzene; 1,2-bis(di-t-butyl-butylphosphinomethyl)-4-(trimethyldecyl)benzene; 1,2-bis(2-phosphine Methyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4,5-diphenylbenzene; 1,2-bis(2-phosphino group Methyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold steel alkyl)-4-phenylbenzene; 1,2-bis(2-phosphinomethyl-1 ,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4,5-bis-(trimethyldecyl)benzene; 1,2-bis(2-phosphine Methyl-1,3,5,7-tetramethyl-6,9,10- Tris-gold steel alkyl)-4-(trimethyldecyl)benzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5-diphenylbenzene; 1,2 - bis(di-gold steel alkylphosphinomethyl)-4-phenylbenzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5-bis-(trimethylnonane) Benzo; 1,2-bis(di-gold-steel alkylphosphinomethyl)-4-(trimethyldecyl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphine Methyl)-2-(di-t-butylphosphinomethyl)-4,5-diphenylbenzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl -2-(di-t-butylphosphinomethyl)-4-phenylbenzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di -T-butylphosphinomethyl)-4,5-bis-(trimethyldecyl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2 -(di-t-butylphosphinomethyl)-4-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6, 9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl) 4,5-diphenylbenzene; 1-(2-phosphinomethyl-1,3 ,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butyl-butylphosphinomethyl)-4-phenylbenzene; 1-(2 -phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold alkane )-2-(di-t-butylphosphinomethyl)-4,5-bis-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3,5,7 -tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4-(trimethyldecyl)benzene; 1-( 2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4, 5-diphenylbenzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold steel Alkylphosphinomethyl)-4-phenylbenzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl) -2-(di-gold-steel alkylphosphinomethyl)-4,5-bis-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl Base-6,9,10-trioxy-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4-(trimethyldecyl)benzene; 1-(di-third- Butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-diphenylbenzene; 1-(di-tertiary-butylphosphino) Base-2-(di-gold-steel alkylphosphinomethyl)-4-phenylbenzene; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphino) -4,5-bis-(trimethyldecyl)benzene; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4- (trimethyldecyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-4,5-diphenylbenzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxacyclohexane -{3. 3. 1. 1[3. 7]} mercapto)-4-phenylbenzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3 . 3. 1. 1[3. 7]} mercapto)-4,5-bis-(trimethyldecyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10 - trioxane -{3. 3. 1. 1[3. 7]} mercapto)-4-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo- {3. 3,1. 1[3. 7]} mercapto)-2-(di-tertiary-butylphosphinomethyl)-4,5-diphenylbenzene; 1-(2-phosphinomethyl-1,3,5-trimethyl Base-6,9,10-trioxytricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)-4-phenylbenzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6 , 9,10-trioxane--3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)-4,5-bis-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1, 3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)-4-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3,5- Trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-diphenylbenzene; 1-(2-phosphinomethyl-1,3,5-trimethyl- 6,9,10-trioxytricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-phenylbenzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9 , 10-trioxane--3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-bis-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3, 5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-(trimethyldecyl)benzene; 1,2-bis-perfluoro(2-phosphinomethyl-1, 3,5,7- Tetramethyl-6,9,10-trioxatriene and {3. 3. 1. 1[3. 7]}-mercapto)-4,5-diphenylbenzene; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10 - trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4-phenylbenzene; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxane Ring and {3. 3. 1. 1[3. 7]}-mercapto)-4,5-bis-(trimethyldecyl)benzene; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl -6,9,10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4-(trimethyldecyl)benzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl)-6 , 9,10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4,5-diphenylbenzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl)-6,9 , 10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4-phenylbenzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetrakis(trifluoro-methyl)-6,9,10- Trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4,5-bis-(trimethyldecyl)benzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl) Base)-6,9,10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4-(trimethyldecyl)benzene; 1,2-bis(di-tertiary-butylphosphinomethyl)-4,5-di-(2'-phenylpropane -2'-yl)benzene; 1,2-bis(di-tertiary-butylphosphinomethyl)-4-(2'-phenylpropan-2'-yl)benzene; 1,2-double ( Di-t-butylphosphinomethyl)-4,5-di-tert-butylbenzene; 1,2-bis(di-tertiary-butylphosphinomethyl)-4-third- Butylbenzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4,5-di- (2'-Phenylpropan-2'-yl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold Steel alkyl)-4-(2'-phenylpropan-2'-yl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9 , 10-trioxo-gold steel alkyl)-4,5-(di-tert-butyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl Base-6,9,10-trioxy-gold steel alkyl)-4-tri-butylbenzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5-di- (2'-Phenylpropan-2'-yl)benzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4-(2'-phenylpropan-2'-yl)benzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5-(di-tertiary-butyl)benzene; 1,2-bis(di-gold steel alkylphosphine) Methyl)-4-tri-butylbenzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl) -4,5-di-(2'-phenylpropan-2'-yl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di- Tert-butylphosphinomethyl)-4-(2'-phenylpropan-2'-yl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)- 2-(di-tert-butylphosphinomethyl)-4,5-(di-tert-butyl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphino) 2-(2-tri-butylphosphinomethyl)-4-tri-butylbenzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl- 6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl) Benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphine Methyl)-4-(2'-phenylpropan-2'-yl)benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10- Tris-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4,5-(di-tert-butyl)benzene; 1-(2-phosphinomethyl- 1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4-tri-butyl Benzene; 1-(2-phosphinomethyl-1,3,5,7- Methyl-6,9,10-trioxy-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl Benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphino Methyl)-4-(2'-phenylpropan-2'-yl)benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-tri Oxygen-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4,5-(di-tert-butyl)benzene; 1-(2-phosphinomethyl-1,3 ,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4-tris-butylbenzene; 1-( Di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)benzene; (di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4-(2'-phenylpropan-2'-yl)benzene; 1-(di- Tertiary-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-(di-tertiary-butyl)benzene; 1-(di-tertiary-butyl Phosphylmethyl)-2-(two gold Steel alkylphosphinomethyl)-4-tris-butylbenzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxane环和-{3. 3. 1. 1[3. 7]} mercapto)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl -6,9,10-trioxytricyclo-{3. 3. 1. 1[3. 7]} mercapto)-4-(2'-phenylpropan-2'-yl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9 , 10-trioxane--3. 3. 1. 1[3. 7]} mercapto)-4,5-(di-tert-butyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10 - trioxane -{3. 3. 1. 1[3. 7]} mercapto)-4-tri-butylbenzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3 . 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1-(2-phosphine Methyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)-4-(2'-phenylpropan-2'-yl)benzene; 1-(2-phosphinomethyl- 1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)-4,5-(di-tertiary-butyl)benzene; 1-(2-phosphinomethyl-1, 3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-tertiary-butylphosphinomethyl)-4-tri-butylbenzene; 1-(2-phosphinomethyl-1,3,5-trimethyl Base-6,9,10-trioxytricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1-(2-phosphinomethyl Base-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-(2'-phenylpropan-2'-yl)benzene; 1-(2-phosphinomethyl-1, 3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-(di-tertiary-butyl)benzene; 1-(2-phosphinomethyl-1,3, 5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-tri-butylbenzene; 1,2-bis-perfluoro(2-phosphinomethyl-1,3, 5,7-tetramethyl-6,9,10-trioxane and {3. 3. 1. 1[3. 7]}-mercapto)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1,2-bis-perfluoro(2-phosphine Methyl-1,3,5,7-tetramethyl-6,9,10-trioxatriene and {3. 3. 1. 1[3. 7]} mercapto)-4-(2'-phenylpropan-2'-yl)benzene; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl Base-6,9,10-trioxane and {3. 3. 1. 1[3. 7]}-mercapto)-4,5-(di-tert-butyl)benzene; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl -6,9,10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4-tert-butylbenzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl)-6,9 , 10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7- Tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3. 3. 1. 1[3. 7]} mercapto)-4-(2'-phenylpropan-2'-yl)benzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro) -Methyl)-6,9,10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4,5-(di-tert-butyl)benzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl) Base)-6,9,10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4-tri-butylbenzene; 1,2-bis(di-tertiary-butylphosphinomethyl)-4,5-diphenyldicyclopentadienyl iron; ,2-bis(di-t-butylphosphinomethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1,2-bis(di-tertiary-butylphosphino) ,4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(di-t-butylphosphinomethyl)-4-(or 1') Trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold lanthanane 1,4,5-diphenyldicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxane - gold steel alkyl)-4-(or 1') phenyl dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6, 9,10-trioxy-gold steel alkyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3, 5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1,2-double ( Di-gold-steel alkylphosphinomethyl)-4,5-diphenyldicyclopentadienyl iron; 1,2-bis(di-gold-steel alkylphosphinomethyl)-4-(or 1') Phenyl dicyclopentadienyl iron; 1,2-bis(di-gold steel alkylphosphino) ,4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(di-gold steel alkylphosphinomethyl)-4-(or 1') (three Methyl decyl) dicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl)- Iron 4,5-diphenyldicyclopentadiene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-tertiary-butylphosphinomethyl) -4-(or 1') phenyl dicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-tertiary-butyl Phosphylmethyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2- (di-t-butylphosphinomethyl)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5 ,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl)-4,5-diphenyldicyclopentadiene Iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphine Methyl)-4-(or 1')phenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10- Trioxo-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4, 5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold Steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl Base-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-diphenyl Dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold steel Alkylphosphinomethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9, 10-trioxo-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(2- Phosphylmethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl)-4- (or 1') (trimethyldecyl) dicyclopentadienyl iron; 1-(di-tertiary-butyl Phosphylmethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-diphenyldicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)- 2-(di-gold-steel alkylphosphinomethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)-2-(di Gold-steel alkylphosphinomethyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)-2-(di Gold iron alkylphosphinomethyl)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5- Trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-4,5-diphenyldicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10- Trioxane and -{3. 3. 1. 1[3. 7]} mercapto)-4-(or 1') phenyl dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9, 10-trioxane--3. 3. 1. 1[3. 7]} mercapto)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl- 6,9,10-trioxytricyclo-{3. 3. 1. 1[3. 7]} mercapto)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6, 9,10-trioxane--3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)-4,5-diphenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3 , 5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1 , 3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphino group Methyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphine Methyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-diphenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5 -Trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]}癸 Base-2-(di-gold-steel alkylphosphinomethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-tri Methyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl -1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis-perfluoro (2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3. 3. 1. 1[3. 7]}-mercapto)-4,5-diphenyldicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl- 6,9,10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4-(or 1') phenyl dicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl -6,9,10-trioxane and {3. 3. 1. 1[3. 7]}-mercapto)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5, 7-Tetramethyl-6,9,10-trioxatriene and {3. 3. 1. 1[3. 7]} mercapto)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis-(2-phosphinomethyl-1,3,5,7- Tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3. 3. 1. 1[3. 7]} mercapto)-4,5-diphenyldicyclopentadienyl iron; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl) )-6,9,10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4-(or 1') phenyl dicyclopentadienyl iron; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro- Methyl)-6,9,10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra (Trifluoro-methyl)-6,9,10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(di-tertiary-butylphosphinomethyl)-4,5 - bis-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(di-t-butylphosphinomethyl)-4-(or 1') ( 2'-Phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(di-tertiary-butylphosphinomethyl)-4,5-di-tertiary-butyl Iron cyclopentadienyl; 1,2-bis(di-tertiary-butylphosphinomethyl)-4- (or 1') iron tris-butyldicyclopentadiene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold Steel alkyl)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5, 7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold steel alkyl)-4,5-(di-tertiary-butyl Dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4- (or 1') tri-butyl dicyclopentadienyl iron; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropane-2 '-yl) dicyclopentadienyl iron; 1,2-bis(di-gold steel alkylphosphinomethyl)-4-(or 1')(2'-phenylpropan-2'-yl) Iron cyclopentadienyl; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1,2-double ( Di-gold-steel alkylphosphinomethyl)-4-(or 1') tris-butyldicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphino) 2-(di-t-butylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(P, P-gold steel alkyl third-butyl Alkylphosphinomethyl)-2-(di-t-butylphosphinomethyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl)-4,5-(di-tertiary-butyl Dicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl)-4- (or 1') tris-butyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl -2-(di-t-butylphosphinomethyl) 4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphino group Methyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl)-4-(or 1') (2'-Phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10 -trioxo-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4,5-(di-tertiary-butyl)dicyclopentane Alkenyl; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butyl Phosphylmethyl)-4-(or 1') tris-butyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9 , 10-trioxo-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadiene Iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphino) 4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl Base-6,9,10-trioxy-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4,5-(di-tertiary-butyl)dicyclopentadiene iron ; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl )-4-(or 1') tri-butyldicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl) -4,5-bis-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)-2-(di-gold lanthanane Phosphinylmethyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)- 2-(two gold Alkylphosphinomethyl)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1-(di-tertiary-butylphosphinomethyl)-2-(di-gold steel Alkylphosphinomethyl)-4-(or 1') tris-butyldicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl- 6,9,10-trioxytricyclo-{3. 3. 1. 1[3. 7]} mercapto)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3, 5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3 , 5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl- 6,9,10-trioxytricyclo-{3. 3. 1. 1[3. 7]} mercapto)-4-(or 1') tris-butyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9, 10-trioxane -{3. 3. 1. 1[3. 7]} mercapto)-2-(di-tertiary-butylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; -(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1-(2-phosphino group Methyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-t-butylphosphinomethyl)-4-(or 1') tris-butyldicyclopentadienyl iron; 1-(2-phosphinomethyl Base-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-( 2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1- (2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl -1,3,5-trimethyl-6,9,10-trioxatricyclo-{3. 3. 1. 1[3. 7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-(or 1') tris-butyldicyclopentadienyl iron; 1,2-bis-perfluoro (2 -phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3. 3. 1. 1[3. 7]}-mercapto)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis-perfluoro (2-phosphinomethyl- 1,3,5,7-tetramethyl-6,9,10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl- 1,3,5,7-tetramethyl-6,9,10-trioxane and {3. 3. 1. 1[3. 7]}-mercapto)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5, 7-Tetramethyl-6,9,10-trioxatriene and {3. 3. 1. 1[3. 7]} mercapto)-4-(or 1') tris-butyldicyclopentadienyl iron; 1,2-bis-(2- Phosphylmethyl-1,3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxatriene and {3. 3. 1. 1[3. 7]} mercapto)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis-(2-phosphinomethyl-1,3 , 5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis-(2-phosphinomethyl-1, 3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxane and {3. 3. 1. 1[3. 7]} mercapto)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; and 1,2-bis-(2-phosphinomethyl-1,3,5,7- Tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3. 3. 1. 1[3. 7]} mercapto)-4-(or 1') tris-butyldicyclopentadienyl iron. The metal complex according to any one of claims 1 to 4, wherein the metal M comprises a noble metal selected from the group consisting of Ru, Rh, Os, Ir, Pt and Pd. The metal complex according to any one of claims 1 to 4, wherein the metal M comprises Ru, Pt or Pd. A catalyst system capable of carbonylating an ethylenically unsaturated compound, which comprises the metal complex of any one of claims 1-6. The catalyst system of claim 7, wherein the metal M comprises a noble metal selected from the group consisting of Ru, Rh, Os, Ir, Pt, and Pd. The catalyst system of claim 7, wherein the metal M comprises Ru, Pt or Pd. A method of preparing a metal complex according to any one of claims 1 to 6, which comprises reacting an amine of metal M with a compound. The method of claim 10, wherein the metal M comprises a noble metal selected from the group consisting of Ru, Rh, Os, Ir, Pt, and Pd. The method of claim 10, wherein the metal M comprises Ru, Pt or Pd. The method of any one of claims 10-12, wherein the phosphine is selected from the group consisting of 1,2-bis-(di-t-butylphosphinomethyl)benzene, 1,2-bis-(di- Third-pentylphosphino Benzo, 1,2-bis-(di-tertiary-butylphosphinomethyl)1,2-bis(di-gold-steel alkylphosphinomethyl)benzene, 1,2-bis(di-3,5-dimethyl fund steel alkylphosphinomethyl)benzene, 1,2-double ( Bi-5-third-buty fund steel alkylphosphinomethyl)benzene, 1,2-bis(1-gold steel alkyl-tert-butyl-phosphinomethyl)benzene, 1-(di gold steel Alkylphosphinomethyl)-2-(di-tertiary-butylphosphinomethyl)benzene, 1-(di-tertiary-butylphosphinomethyl)-2-(di-adamantylphosphine) Methyl)benzene, 1-(di-t-butylphosphinomethyl)-2-(phosphorus-gold-steel alkyl-P-methyl)benzene, 1-(di-gold-steel alkylphosphino) Base)-2-(phosphorus-gold steel alkyl-P-methyl)benzene, 1-(third-butane fund steel alkylphosphinomethyl)-2-(di-gold steel alkylphosphinomethyl Benzene and 1-[(P-(2,2,6,6,-tetra-methylphosphino-4-one)phosphinomethyl)]-2-(phosphorus-gold steel alkyl-P- Benzene, wherein "phosphorus-gold steel alkyl" is selected from 2-phosphorus-1,3,5,7-tetramethyl-6,9,10-trioxy gold steel alkyl, 2-phosphorus-1 , 3,5-trimethyl-6,9,10 trioxy gold steel alkyl, 2-phosphorus-1,3,5,7-tetrakis(trifluoromethyl)-6,9,10-trioxy gold Steel alkyl or 2-phosphorus-1,3,5-tris(trifluoromethyl)-6,9,10-trioxy gold steel alkyl; 1,2-bis-(dimethylaminomethyl) Cyclopentadienyl iron, 1,2-bis-(di-t-butylphosphino) Dicyclopentadienyl iron, 1-hydroxymethyl-2-dimethylaminomethyldicyclopentadienyl iron, 1,2-bis-(di-t-butylphosphinomethyl)dicyclopentane Diene iron, 1-hydroxymethyl-2,3-bis-(dimethylaminomethyl)dicyclopentadienyl iron, 1,2,3-para-(di-tert-butylphosphinomethyl) Iron dicyclopentadiene, iron 1,2-bis-(dicyclohexylphosphinomethyl)dicyclopentadiene, 1,2-bis-(di-isobutylphosphinomethyl)dicyclopentan Iron diene, 1,2-bis-(dicyclopentylphosphinomethyl)dicyclopentadienyl iron, 1,2-bis-(diethylphosphinomethyl)dicyclopentadienyl iron, 1 , 2-bis(di-isopropylphosphinomethyl)dicyclopentadienyl iron, 1,2-bis-(dimethylphosphinomethyl)dicyclopentadienyl iron, 1,2-double- (bis-(1,3,5,7-tetramethyl-6,9,10-trioxo-2-phosphorus-gold steel alkylmethyl)) dicyclopentadienyl iron, 1,2-double- (dimethylaminomethyl)dicyclopentadienyl iron-diiodide Methane, 1,2-bis(dihydroxymethylphosphinomethyl)dicyclopentadienyl iron, 1,2-bis(diphosphinomethyl)dicyclopentadienyl iron, 1,2-double- α,α-(P-(2,2,6,6,-Tetramethylphosphino-4-one)) dimethyldicyclopentadienyl iron and 1,2-bis-(di-1,3 ,5,7-tetramethyl-6,9,10-trioxo-2-phosphorus-gold steel alkylmethyl))benzene; cis-1,2-bis(di-tertiary-butylphosphino) Methyl)-4,5-dimethylcyclohexane; cis-1,2-bis(di-t-butyl-butylphosphinomethyl)-5-methylcyclopentane; cis-1, 2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold steel alkyl)-4,5-dimethylcyclohexane; Formula-1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl) 5-methylcyclopentane; Formula-1,2-bis(di-gold steel alkylphosphinomethyl)-4,5-dimethylcyclohexane; cis-1,2-bis(di-gold steel alkylphosphinomethyl) -5-methylcyclopentane; cis-1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl)- 4,5-Dimethylcyclohexane; cis-1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl) )-5-methylcyclopentane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl- 6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4,5-dimethylcyclohexane; cis-1-(2- Phosphylmethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-5- Methylcyclopentane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(two Gold steel alkylphosphinomethyl)-5-methylcyclohexane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-tri Oxygen-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-5-methylcyclopentane; cis-1-(2-phosphinomethyl-1,3,5,7 -tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)cyclobutane; cis-1-(di-tertiary-butyl Phosphylmethyl)-2-(digold steel alkylphosphinomethyl)-4,5-dimethylcyclohexane; cis-1-(di-tertiary-butylphosphinomethyl)- 2-(di-gold-steel alkylphosphinomethyl)-5-methylcyclopentane; cis-1,2-bis(2-phosphorus-1,3,5-three Methyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4,5-dimethylcyclohexane; cis-1,2-bis(2-phosphorus -1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-5-methylcyclopentane; cis-1-(2 -phosphorus-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphino) Base)-4,5-dimethylcyclohexane; cis-1-(2-phospho-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1 [3.7]} mercapto)-2-(di-tertiary-butylphosphinomethyl)-5-methylcyclopentane; cis-1-(2-phosphorus-1,3,5-trimethyl Base-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-dimethylcyclohexane ;cis-1-(2-phospho-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(two gold Steel alkylphosphinomethyl)-5-methylcyclopentane; cis-1,2-bis-perfluoro(2-phosphorus-1,3,5,7-tetramethyl-6,9,10 - trioxane and {3.3.1.1[3.7]}-mercapto)-4,5-dimethylcyclohexane; cis-1,2-bis-perfluoro(2-phosphorus-1,3, 5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-5-methylcyclopentane; cis-1,2-bis-(2 -phosphorus-1,3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxane Cyclo [3.3.1.1 [3.7]} fluorenyl)-4,5-dimethylcyclohexane; cis-1,2-bis-(2-phosphorus-1,3,5,7-tetra (three Fluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-5-methylcyclopentane; cis-1,2-bis(di-third -butylphosphinomethyl)cyclohexane; cis-1,2-bis(di-tertiary-butylphosphinomethyl)cyclopentane; cis-1,2-bis(di-third -butylphosphinomethyl)cyclobutane; cis-1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold Steel alkyl) cyclohexane; cis-1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl) Cyclopentane; cis-1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)cyclobutane; Cis-1,2-bis(di-gold steel alkylphosphinomethyl)cyclohexane; cis-1,2-bis(di-gold steel alkylphosphinomethyl)cyclopentane; cis -1,2-bis(di-gold steel alkylphosphinomethyl)cyclobutane; cis-1-(P,P-gold steel alkyl Tri-butyl-phosphinomethyl)-2-(di-t-butylphosphinomethyl)cyclohexane; cis-1-(P,P-gold steel alkyl-tert-butyl- Phosphylmethyl)-2-(di-t-butylphosphinomethyl)cyclopentane; cis-1-(P,P-gold steel alkyl-tert-butyl-phosphinomethyl) -2-(di-t-butylphosphinomethyl)cyclobutane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10 -trioxo-gold steel alkyl)-2-(di-t-butylphosphinomethyl)cyclohexane; cis-1-(2-phosphinomethyl-1,3,5,7- Tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl)cyclopentane; cis-1-(2-phosphinomethyl -1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl)cyclobutane; cis- 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl) Cyclohexane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold steel Alkylphosphinomethyl)cyclopentane; cis-1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl) -2-(di-gold-steel alkylphosphinomethyl)cyclobutane; cis-1-(di-tertiary-butylphosphinomethyl)-2 -(二金钢alkylphosphinomethyl)cyclohexane; cis-1-(di-tertiary-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)cyclopentane Alkane; cis-1-(di-tertiary-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)cyclobutane; cis-1,2-bis(2-phosphorus -1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)cyclohexane; cis-1,2-bis(2-phosphorus -1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)cyclopentane; cis-1,2-bis(2-phosphorus -1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)cyclobutane; cis-1-(2-phospho-1, 3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)cyclohexane ;cis-1-(2-phospho-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di- Tert-butylphosphinomethyl)cyclopentane; cis-1-(2-phospho-1,3,5-trimethyl-6,9,10-trioxatricyclo -{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)cyclobutane; cis-1-(2-phosphorus-1,3,5-trimethyl -6,9,10-trioxatricyclo-{3.3.1.1[3.7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)cyclohexane; cis-1-(2 -phosphorus-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl) Cyclopentane; cis-1-(2-phospho-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2- (two gold steel alkylphosphinomethyl)cyclobutane; cis-1,2-bis-perfluoro(2-phosphorus-1,3,5,7-tetramethyl-6,9,10-three Oxytricyclo and {3.3.1.1[3.7]}-mercapto)cyclohexane; cis-1,2-bis-perfluoro(2-phosphino-1,3,5,7-tetramethyl-6, 9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)cyclopentane; cis-1,2-bis-perfluoro(2-phosphorus-1,3,5,7-tetramethyl -6,9,10-trioxatricyclo and {3.3.1.1[3.7]} fluorenyl)cyclobutane; cis-1,2-bis-(2-phosphine-1,3,5,7- Tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)cyclohexane; cis-1,2-bis-(2-phosphor-1 , 3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)cyclopentane; cis-1,2-double -(2-Phosphorus-1,3,5,7-tetrakis(trifluoro-methyl)-6,9,10-three Tricyclic and {3.3.1.1[3.7]}indenyl)cyclobutane; (2-exoordinary, 3-external)-bicyclo[2.2.1]heptane-2,3-bis(di-third-butyl) (phosphinomethyl); (2-introvert, 3-intro)-bicyclo[2.2.1]heptane-2,3-bis(di-t-butylphosphinomethyl); 1,2- Bis(di-tert-butylphosphinomethyl)-4,5-diphenylbenzene; 1,2-bis(di-tertiary-butylphosphinomethyl)-4-phenylbenzene; ,2-bis(di-t-butylphosphinomethyl)-4,5-bis-(trimethyldecyl)benzene; 1,2-bis(di-tertiary-butylphosphinomethyl) -4-(trimethyldecyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold lanthanane 1,4,5-diphenylbenzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl -4-phenylbenzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4, 5-bis-(trimethyldecyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10- Tris-gold steel alkyl)-4-(trimethyldecyl)benzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5-diphenylbenzene; 1,2 - bis(di-gold steel alkylphosphinomethyl)-4-phenylbenzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5-bis-(trimethylnonane) Benzo; 1,2-bis(di-gold-steel alkylphosphinomethyl)-4-(trimethyldecyl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphine Methyl)-2-(di-t-butylphosphinomethyl)-4,5-diphenylbenzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl -2-(di-t-butylphosphinomethyl)-4-phenylbenzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di -T-butylphosphinomethyl)-4,5-bis-(trimethyldecyl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2 -(di-t-butylphosphinomethyl)-4-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6, 9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl) 4,5-diphenylbenzene; 1-(2-phosphinomethyl-1,3 ,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butyl-butylphosphinomethyl)-4-phenylbenzene; 1-(2 -phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold alkane )-2-(di-t-butylphosphinomethyl)-4,5-bis-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3,5,7 -tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4-(trimethyldecyl)benzene; 1-( 2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4, 5-diphenylbenzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold steel Alkylphosphinomethyl)-4-phenylbenzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl) -2-(di-gold-steel alkylphosphinomethyl)-4,5-bis-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl Base-6,9,10-trioxy-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4-(trimethyldecyl)benzene; 1-(di-third- Butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-diphenylbenzene; 1-(di-tertiary-butylphosphino) Base-2-(di-gold-steel alkylphosphinomethyl)-4-phenylbenzene; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphino) -4,5-bis-(trimethyldecyl)benzene; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4- (trimethyldecyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7 ]} mercapto)-4,5-diphenylbenzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo- {3.3.1.1[3.7]} mercapto)-4-phenylbenzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxane Cyclo-{3.3.1.1[3.7]}mercapto)-4,5-bis-(trimethyldecyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5-tri Methyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1, 3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)-4, 5-diphenylbenzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]} mercapto) -2-(di-t-butylphosphinomethyl)-4-phenylbenzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-tri Oxygen tricyclic -{3.3.1.1 [3.7]} mercapto)-2-(di-tert-butylphosphinomethyl)-4,5-bis-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1 ,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)-4 -(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]} Mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-diphenylbenzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9 , 10-trioxocyclo-{3.3.1.1[3.7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-phenylbenzene; 1-(2-phosphinomethyl -1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4 , 5-bis-(trimethyldecyl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1 [3.7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-(trimethyldecyl)benzene; 1,2-bis-perfluoro(2-phosphinomethyl-1 ,3,5,7- Tetramethyl-6,9,10-trioxatricyclo{3.3.1.1[3.7]}-mercapto)-4,5-diphenylbenzene; 1,2-bis-perfluoro(2-phosphino) Methyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4-phenylbenzene; 1,2-double- Perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}-mercapto)-4,5- Bis-(trimethyldecyl)benzene; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxacyclohexane {3.3.1.1 [3.7]} mercapto)-4-(trimethyldecyl)benzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro- Methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4,5-diphenylbenzene; 1,2-bis-(2-phosphinomethyl- 1,3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4-phenylbenzene; 1,2- Bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}indenyl)- 4,5-bis-(trimethyldecyl)benzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl)-6,9, 10-trioxotricyclo{3.3.1.1[3.7]}mercapto)-4-(trimethyldecyl)benzene; 1,2-bis(di-t-butylphosphinomethyl)-4 ,5-di-(2'-phenylpropan-2'-yl)benzene; 1,2-bis(di-third-butyl) Phosphylmethyl)-4-(2'-phenylpropan-2'-yl)benzene; 1,2-bis(di-tertiary-butylphosphinomethyl)-4,5-di-third -butylbenzene; 1,2-bis(di-t-butyl-butylphosphinomethyl)-4-tri-butylbenzene; 1,2-bis(2-phosphinomethyl-1,3, 5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1,2-double ( 2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4-(2'-phenylpropan-2'-yl)benzene ; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4,5-(di-third -butyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4-third -butylbenzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1,2-double ( Di-gold-steel alkylphosphinomethyl)-4-(2'-phenylpropan-2'-yl)benzene; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5 -(di-tert-butyl)benzene; 1,2-bis(di-gold steel alkylphosphine) Methyl)-4-tri-butylbenzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl) -4,5-di-(2'-phenylpropan-2'-yl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di- Tert-butylphosphinomethyl)-4-(2'-phenylpropan-2'-yl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)- 2-(di-tert-butylphosphinomethyl)-4,5-(di-tert-butyl)benzene; 1-(P,P-gold steel alkyl-tert-butylphosphino) 2-(2-tri-butylphosphinomethyl)-4-tri-butylbenzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl- 6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl) Benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphine Methyl)-4-(2'-phenylpropan-2'-yl)benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10- Tris-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4,5-(di-tert-butyl)benzene; 1-(2-phosphinomethyl- 1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4-tri-butyl Benzene; 1-(2-phosphinomethyl-1,3,5,7- Methyl-6,9,10-trioxy-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl Benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphino Methyl)-4-(2'-phenylpropan-2'-yl)benzene; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-tri Oxygen-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4,5-(di-tert-butyl)benzene; 1-(2-phosphinomethyl-1,3 ,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4-tris-butylbenzene; 1-( Di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)benzene; (di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4-(2'-phenylpropan-2'-yl)benzene; 1-(di- Tertiary-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-(di-tertiary-butyl)benzene; 1-(di-tertiary-butyl Phosphylmethyl)-2-(two gold Steel alkylphosphinomethyl)-4-tris-butylbenzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxane Cyclo-{3.3.1.1[3.7]}mercapto)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1,2-bis(2-phosphinomethyl-1 ,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4-(2'-phenylpropan-2'-yl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4,5 -(di-tert-butyl)benzene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3. 1.1[3.7]} mercapto)-4-tert-butylbenzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo- {3.3.1.1 [3.7]} mercapto)-2-(di-t-butylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)benzene; -(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-third -butylphosphinomethyl)-4-(2'-phenylpropan-2'-yl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9, 10-trioxotricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)-4,5-(di-t-butyl)benzene ; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}癸2-(2-tris-butylphosphinomethyl)-4-tri-butylbenzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6, 9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropane- 2'-yl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]} mercapto) -2-(di-gold-steel alkylphosphinomethyl)-4-(2'-phenylpropan-2'-yl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl Base-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-(di-third- Butyl)benzene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}indenyl)-2 -(二金钢alkylphosphinomethyl)-4-tri-butylbenzene; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl- 6,9,10-trioxatricyclo and {3.3.1.1[3.7]}-mercapto)-4,5-di-(2'-phenylpropan-2'-yl)benzene; 1,2-double -Perfluoro(2-phosphine Methyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo{3.3.1.1[3.7]}mercapto)-4-(2'-phenylpropan-2- '-yl)benzene; 1,2-bis-perfluoro (2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[ 3.7]}-mercapto)-4,5-(di-tert-butyl)benzene; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl -6,9,10-trioxotane and {3.3.1.1[3.7]}mercapto)-4-tri-butylbenzene; 1,2-bis-(2-phosphinomethyl-1,3 ,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4,5-di-(2'-phenylpropane -2'-yl)benzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxacyclohexane {3.3.1.1[3.7]} mercapto)-4-(2'-phenylpropan-2'-yl)benzene; 1,2-bis-(2-phosphinomethyl-1,3,5,7 -tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4,5-(di-tertiary-butyl)benzene; 2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]} fluorenyl -4-tri-butylbenzene; 1,2-bis(di-tertiary-butylphosphinomethyl)-4,5-diphenyldicyclopentadienyl iron; 1,2-double ( Di-t-butylphosphinomethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1,2-bis(di-third-butyl) Phosphinylmethyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(di-tertiary-butylphosphinomethyl)-4- (or 1') (trimethyldecyl) dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxane - gold steel alkyl)-4,5-diphenyldicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9, 10-trioxo-gold steel alkyl)-4-(or 1')phenyl dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl Base-6,9,10-trioxy-gold steel alkyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl- 1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 2-bis(di-gold steel alkylphosphinomethyl)-4,5 diphenyldicyclopentadienyl iron; 1,2-bis(di-gold steel alkylphosphinomethyl)-4-( Or 1') phenyl dicyclopentadienyl iron; 1,2-bis(di-gold steel alkylphosphine ,4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(di-gold steel alkylphosphinomethyl)-4-(or 1') (three Methyl decyl) dicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl)- Iron 4,5-diphenyldicyclopentadiene; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-tertiary-butylphosphinomethyl) -4-(or 1') phenyl dicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-tertiary-butyl Phosphylmethyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2- (di-t-butylphosphinomethyl)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5 ,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl)-4,5-diphenyldicyclopentadiene Iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butylphosphine Methyl)-4-(or 1')phenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10- Trioxo-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4, 5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold Steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl Base-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-diphenyl Dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold steel Alkylphosphinomethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9, 10-trioxo-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(2- Phosphylmethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl)-4- (or 1') (trimethyldecyl) dicyclopentadienyl iron; 1-(di-tertiary-butyl Phosphylmethyl)-2-(di-gold-steel alkylphosphinomethyl)-4,5-diphenyldicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)- 2-(di-gold-steel alkylphosphinomethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)-2-(di Gold-steel alkylphosphinomethyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)-2-(di Gold iron alkylphosphinomethyl)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5- Trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4,5-diphenyldicyclopentadienyl iron; 1,2-bis(2- Phosphylmethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4-(or 1')phenyl bicyclo Iron pentadiene; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]} fluorenyl -4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10 - trioxocyclo-{3.3.1.1[3.7]}mercapto)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl- 1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-( Di-t-butylphosphinomethyl)-4,5-diphenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9 , 10-trioxocyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)-4-(or 1')phenyldicyclopentane Alkene iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-( Di-t-butylphosphinomethyl)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-tri Methyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)-4-(or 1') (trimethyldecyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1 [3.7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-diphenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3, 5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}癸 Base-2-(di-gold-steel alkylphosphinomethyl)-4-(or 1')phenyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-tri Methyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4,5-bis-(trimethyl矽alkyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7] }癸))-2-(di-gold-steel alkylphosphinomethyl)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis-perfluoro (2 -phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}-mercapto)-4,5-diphenyl Iron cyclopentadienyl; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[ 3.7]} mercapto)-4-(or 1') phenyl dicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl -6,9,10-trioxatricyclo{3.3.1.1[3.7]}-mercapto)-4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-double - perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4-(or 1') (trimethyldecyl) dicyclopentadienyl iron; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl)-6, 9,10-trioxane Cyclo [3.3.1.1 [3.7]} fluorenyl)-4,5-diphenyldicyclopentadienyl iron; 1,2-bis-(2-phosphinomethyl-1,3,5,7- Tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4-(or 1')phenyldicyclopentadienyl iron; 2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]} fluorenyl -4,5-bis-(trimethyldecyl)dicyclopentadienyl iron; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl) ,6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4-(or 1')(trimethyldecyl)dicyclopentadienyl iron; 1,2 - bis(di-t-butylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(di- Tertiary-butylphosphinomethyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(di-third-butyl) Isophosphinylmethyl)-4,5-di-tert-butyldicyclopentadienyl iron: 1,2-bis(di-tertiary-butylphosphinomethyl)-4- (or 1') iron tris-butyldicyclopentadiene; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold Steel alkyl)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5, 7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxo-gold steel alkyl)-4,5-(di-tertiary-butyl Dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-4- (or 1') tri-butyl dicyclopentadienyl iron; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropane-2 '-yl) dicyclopentadienyl iron; 1,2-bis(di-gold steel alkylphosphinomethyl)-4-(or 1')(2'-phenylpropan-2'-yl) Iron cyclopentadienyl; 1,2-bis(di-gold steel alkylphosphinomethyl)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1,2-double ( Di-gold-steel alkylphosphinomethyl)-4-(or 1') tris-butyldicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphino) 2-(di-t-butylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(P, P-gold steel alkyl third-butyl Alkylphosphinomethyl)-2-(di-t-butylphosphinomethyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl)-4,5-(di-tertiary-butyl Dicyclopentadienyl iron; 1-(P,P-gold steel alkyl-tert-butylphosphinomethyl)-2-(di-t-butylphosphinomethyl)-4- (or 1') tris-butyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl -2-(di-t-butylphosphinomethyl) 4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphino group Methyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-t-butylphosphinomethyl)-4-(or 1') (2'-Phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10 -trioxo-gold steel alkyl)-2-(di-tertiary-butylphosphinomethyl)-4,5-(di-tertiary-butyl)dicyclopentane Alkenyl; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-tertiary-butyl Phosphylmethyl)-4-(or 1') tris-butyldicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9 , 10-trioxo-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadiene Iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphino) 4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl Base-6,9,10-trioxy-gold steel alkyl)-2-(digold steel alkylphosphinomethyl)-4,5-(di-tertiary-butyl)dicyclopentadiene iron ; 1-(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxy-gold steel alkyl)-2-(di-gold-steel alkylphosphinomethyl )-4-(or 1') tri-butyldicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)-2-(di-gold-steel alkylphosphinomethyl) -4,5-bis-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)-2-(di-gold lanthanane Phosphinylmethyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(di-t-butylphosphinomethyl)- 2-(two gold Alkylphosphinomethyl)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1-(di-tertiary-butylphosphinomethyl)-2-(di-gold steel Alkylphosphinomethyl)-4-(or 1') tris-butyldicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl- 6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4-( Or 1') (2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis(2-phosphinomethyl-1,3,5-trimethyl-6,9 , 10-trioxocyclo-{3.3.1.1[3.7]}mercapto)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1,2-bis(2-phosphine Methyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-4-(or 1')tri-butyl Dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxacyclohexane -{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)-4,5-di-(2'-phenylpropan-2'-yl)bicyclo Iron pentadiene; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}indenyl)-2 -(di-t-butylphosphinomethyl)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphino 1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-tertiary-butylphosphinomethyl) -4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxane Tricyclic-{3.3.1.1[3.7]}mercapto)-2-(di-t-butylphosphinomethyl)-4-(or 1') tert-butyldicyclopentadienyl iron ; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(two gold Steel alkylphosphinylmethyl)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5 -trimethyl-6,9,10-trioxatricyclo-{3.3.1.1[3.7]}mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-(or 1') (2'-Phenylpropan-2'-yl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9,10-trioxane And -{3.3.1.1[3.7]}癸基)-2-(two gold steel Phosphinylmethyl)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1-(2-phosphinomethyl-1,3,5-trimethyl-6,9 , 10-trioxocyclo-{3.3.1.1[3.7]} mercapto)-2-(di-gold-steel alkylphosphinomethyl)-4-(or 1') tri-butyldicyclopentane Diene iron; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7] }-mercapto)-4,5-di-(2'-phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl-1, 3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4-(or 1')(2'-phenylpropane-2' -yl)dicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo) 3.3.1.1[3.7]}-mercapto)-4,5-(di-tertiary-butyl)dicyclopentadienyl iron; 1,2-bis-perfluoro(2-phosphinomethyl-1, 3,5,7-tetramethyl-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4-(or 1') tris-butyldicyclopentadiene Iron; 1,2-double-(2- Phosphylmethyl-1,3,5,7-tetrakis(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7]}mercapto)-4,5-di -(2'-Phenylpropan-2'-yl)dicyclopentadienyl iron; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl) )-6,9,10-trioxane and {3.3.1.1[3.7]}mercapto)-4-(or 1')(2'-phenylpropan-2'-yl)dicyclopentadiene Iron; 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra(trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1[3.7 ]} mercapto)-4,5-(di-tri-butyl)dicyclopentadienyl iron; and 1,2-bis-(2-phosphinomethyl-1,3,5,7-tetra (Trifluoro-methyl)-6,9,10-trioxatricyclo and {3.3.1.1 [3.7]} mercapto)-4-(or 1') tris-butyldicyclopentadienyl iron. The method of any one of claims 10-12, wherein the amount of the compound of the compound in the reaction mixture is calculated to provide a molar excess of at least 10% of the amount required for the stoichiometric reaction. The method of claim 14, wherein the reacting is carried out in the presence of a solvent. A method for the carbonylation of an ethylenically unsaturated compound, comprising reacting the compound with carbon monoxide in the presence of a source of a hydroxyl group and a catalytic system, the catalyst system comprising any one of claims 1-6 Metal complex.